WorldWideScience

Sample records for high-mobility solvent anions

  1. Improvement of Anion Transport Systems by Modulation of Chalcogen Interactions: The influence of solvent.

    Science.gov (United States)

    Sánchez-Sanz, Goar; Trujillo, Cristina

    2018-02-08

    A series of potential anion transporters, dithieno[3,2-b;2',3'-d]thiophenes (DTT), involving anion-chalcogen interactions have been studied by analyzing the interaction energy, geometry, and charge transfer. It was found that gas phase calculations show very negative interaction energies with short anion-chalcogen distances, but when solvent effects are considered, the interaction energy values decreased drastically concomitantly with an elongation on the interatomic distances. To enhance the chalcogen interaction between the DTT derivatives and the anion, increasing the anion transporter capacity, bisisothioazole moiety was considered; i.e., the σ-hole of the chalcogen atom was modulated by substitution of the adjacent carbon by a nitrogen atom in the S-C axis, increasing the depth of the σ-hole and therefore the interaction between the chalcogen and anion. Finally, different anions were analyzed within the complexes, finding that F - and NO 3 - would be the best candidates to form complexes and possibly displace other anions such as Cl - or Br - .

  2. The strong influence of the solvent on the electron spin resonance spectra of semiquinone radical anions

    DEFF Research Database (Denmark)

    Spanget-Larsen, Jens

    2013-01-01

    ). The proton hyperfine constants predicted for the chrysazin semiquinone radical anion were highly sensitive to the assumed dielectric constant ε of the solvent continuum, inverting the relative magnitudes of the hyperfine constants and thereby leading to agreement with the observed data published by Stegmann...

  3. Cluster structure of imidazolium salts in methanol controlled by the balance of interactions: cation-anion, cation-solvent, and anion-solvent.

    Science.gov (United States)

    Kitaoka, Satoshi; Nobuoka, Kaoru; Ishikawa, Yuichi; Wakisaka, Akihiro

    2008-10-01

    We have studied the cluster structure of 1-butyl-3-methylimidazolium halide, bmimX (X = Cl, Br, I), in methanol solution by means of an electrospray mass spectrometer, which is specially designed for analysis of clusters isolated from solution. In positive ion mode experiments, the ratio of solvated bmim(+), bmim(+)(MeOH)(n) and ion-pair clusters, bmim(bmim(+)X(-))(m) was dependent on the counter anion. As for bmimCl solutions, few solvated bmim(+) clusters were observed, and the ion-pair clusters were clearly observed. On the other hand, bmimBr and bmimI with large anions, the solvated bmim(+) clusters increased obviously, and the ion-pair clusters were in turn remarkably decreased. In negative ion-mode experiments, the solvation for Br(-) by the methanol is found to be the most prominent among those for Cl(-), Br(-), and I(-). These results were reasonably explained in consideration of the balance between ion-solvent and ion-counterion interactions.

  4. 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.

  5. Tunable multicolor emissions in a monocomponent gel system by varying the solvent, temperature and fluoride anion.

    Science.gov (United States)

    Pang, Xuelei; Yu, Xudong; Xie, Dongyan; Li, Yajuan; Geng, Lijun; Ren, Jujie; Zhen, Xiaoli

    2016-11-29

    The facile tuning of the fluorescent properties of organogels is highly desirable for optical switches, light-emitting diodes, chemosensors and bioprobes. The design of organic molecules with multiple emission colors but only one molecular platform remains challenging. Herein, a new cholesterol-based organogelator N1 containing D-A pairs (salicylaldehyde and naphthalimide units) was designed. We successfully obtained multiple solvent-tuned emission colors in both the solution and gel states using a unimolecular platform. Moreover, the effects of the solvent on the gel morphology, rheology and anion-responsive properties were studied. Finally, we showed that the gel in benzene displayed reversible thermochromic properties with changes in emission color from yellow-green to red. Several experiments suggested that a short-distance and ordered array of the D-A pairs facilitated the efficient intermolecular electron transfer of the fluorophores.

  6. Reversible rearrangements of Cu(II) cage complexes: solvent and anion influences.

    Science.gov (United States)

    Bernhardt, Paul V; Font, Helena; Gallego, Carlos; Martínez, Manuel; Rodríguez, Carlos

    2012-11-19

    The macrobicyclic mixed donor cage ligand AMME-N3S3sar (1-methyl-8-amino-3,13,16-trithia-6,10,19-triazabicyclo[6.6.6]eicosane) is capable of binding to Cu(II) as either a hexadentate (N3S3) or tetradentate (N2S2) ligand. The "Cu-in" (hexadentate)/"Cu-out" (tetradendate) equilibrium for the {Cu(AMME-N3S3sar)}(2+) units is strongly influenced by both solvent (DMSO, MeCN, and water) and halide ions (Br(-) and Cl(-)). We have established a crucial role of the solvent in these processes through the formation of intermediate solvato complexes, which are substituted by incoming halide ions triggering a final isomerization reaction. Surprisingly, for reactions carried out in the usually strongly coordinating solvent water, the completely encapsulated N3S3-bound "Cu-in" form is dominant. Furthermore, the small amounts of the "Cu-out" form present in equilibrated DMSO or MeCN solutions revert entirely to the "Cu-in" form in aqueous media, thus preventing reaction with halide anions which otherwise lead to partial or even complete decomposition of the complex. From the kinetic, electrochemical, and EPR results, the existence of an outer-sphere H-bonded network of water molecules interacting with the complex inhibits egress of the Cu(II) ion from the cage ligand. This is extremely relevant in view of outer sphere interactions present in strongly hydrogen bonding solvents and their effects on Cu(II) complexation.

  7. The role of anions, solvent molecules and solvated electrons in layer formation processes on anode materials for rechargeable lithium batteries

    Energy Technology Data Exchange (ETDEWEB)

    Rahner, D. [Technische Univ. Dresden (Germany). Inst. fuer Physikalische Chemie und Elektrochemie

    1999-09-01

    The reactivity of anions, solvent molecules and solvated electrons against anode materials are coupled in a given electrolyte solution. The ratio between anion and solvent decomposition depends on the potential and the electrolyte composition. The life time of trapped solvated electrons within the growing SEI layer depends on the donor-acceptor properties of the incorporated solvent molecules and is in the range among 3-10 s. The places of the trapped electrons are the origin of 'metallic' lithium clusters within the forming layer. Their growth will lead to the well-known lithium dendrites on lithium-metal or the progressive irreversible capacity loss on lithium-carbons and therefore causes a lot of problems. Suggestions will be made how to solve these problems in order to achieve a homogeneous SEI with a reduced dendrite growth or decreased irreversible capacity loss. (orig.)

  8. Zwitterion radicals and anion radicals from electron transfer and solvent condensation with the fingerprint developing agent ninhydrin.

    Science.gov (United States)

    Schertz, T D; Reiter, R C; Stevenson, C D

    2001-11-16

    Ninhydrin (the fingerprint developing agent) spontaneously dehydrates in liquid ammonia and in hexamethylphosphoramide (HMPA) to form indantrione, which has a sufficiently large solution electron affinity to extract an electron from the solvent (HMPA) to produce the indantrione anion radical. In liquid NH(3), the presence of trace amounts of amide ion causes the spontaneous formation of an anion radical condensation product, wherein the no. 2 carbon (originally a carbonyl carbon) becomes substituted with -NH(2) and -OH groups. In HMPA, the indantrione anion radical spontaneously forms condensation products with the HMPA to produce a variety of zwitterionic radicals, wherein the no. 2 carbon becomes directly attached to a nitrogen of the HMPA. The mechanisms for the formation of the zwitterionic paramagnetic condensation products are analogous to that observed in the reaction of ninhydrin with amino acids to yield Ruhemann's Purple, the contrast product in fingerprint development. The formation of anion and zwitterionic radical condensation products from ninhydrin and nitrogen-containing solvents may represent an example of a host of analogous polyketone-solvent reactions.

  9. Physicochemical characterisation and antimicrobial phototoxicity of an anionic porphyrin in natural deep eutectic solvents.

    Science.gov (United States)

    Wikene, Kristine Opsvik; Rukke, Håkon Valen; Bruzell, Ellen; Tønnesen, Hanne Hjorth

    2016-08-01

    Natural deep eutectic solvents (NADES) are a newly discovered group of eutectics which has shown promise as a solvent in antimicrobial photodynamic therapy (aPDT). The purpose of this study was to investigate preparations of an anionic porphyrin, meso-tetra-(4-carboxyphenyl)-porphine (TCPP), solubilised in NADES, with regard to their physicochemical and antibacterial properties. The NADES CS (pH∼0), ChX (pH∼4) and MFG (pH∼1) solubilised TCPP with absorption maximum ∼443nm and emission maximum ∼678nm, indicating formation of the TCPP dication. Dilution of TCPP-NADES>1:1 (water) reduced the physical stability of the preparations. The photostability half-lives of TCPP in methanol, MFG, and CS were ∼9h, 6.9h and 3.2h, respectively. Nanomolar concentrations of TCPP solubilised in diluted MFG combined with ⩽27J/cm(2) blue light increased Gram-positive and Gram-negative bacterial phototoxicity, >99.98% and 96% bacterial reduction, respectively, compared to TCPP in PBS/ethanol under equivalent treatment conditions. TCPP solubilised in diluted CS was toxic to bacteria both in the absence (36-72% reduction) and presence of light. TCPP in CS, and in the CS component citric acid, induced a TCPP-concentration dependent increase in Gram-negative phototoxicity relative to controls, which was most pronounced for TCPP-CS. The mechanism behind the increased toxicity is unknown. Copyright © 2016 Elsevier B.V. All rights reserved.

  10. Preferential solvation of ions in mixed solvents. 6: Univalent anions in aqueous organic solvents according to the inverse Kirkwood-Buff integral (IKBI) approach

    Energy Technology Data Exchange (ETDEWEB)

    Marcus, Yizhak [Department of Inorganic and Analytical Chemistry, Hebrew University of Jerusalem, Jerusalem 91904 (Israel)], E-mail: ymarcus@vms.huji.ac.il

    2007-10-15

    The inverse Kirkwood-Buff integral (IKBI) approach is applied to the preferential solvation of F{sup -}, Cl{sup -}, Br{sup -}, I{sup -}, and ClO{sub 4}{sup -} in aqueous mixtures of the co-solvents (S) methanol (MeOH), ethanol (EtOH), t-butanol (t-BuOH), 1,2-ethanediol (EG), glycerol (Gly), acetone (Me{sub 2}CO), acetonitrile (MeCN), formamide (FA), N,N-dimethylformamide (DMF), N,N,N',N',N'',N''-hexamethyl phosphoric triamide (HMPT), and dimethylsulfoxide (DMSO), as far as the relevant data exist in the literature. Fluoride anions are selectively solvated by the water up to large mole fractions (x{sub S} {>=} 0.4) of S = EtOH, t-BuOH, Me{sub 2}CO, MeCN, and DMF, and up to lower contents (x{sub S} {approx} 0.1) of MeOH, EG, FA, and DMSO. The other anions are preferentially solvated by water to diminishing extent as their sizes become larger, and the largest ones show some preference for S in water-rich mixtures of MeOH and FA, whereas in aqueous Gly even chloride is preferentially solvated by the Gly. The competition between the co-solvent and the anion for the hydrogen bonds that water molecules donate is the main cause for the observed preferential solvation behaviour.

  11. Micellar partitioning and its effects on Henry's law constants of chlorinated solvents in anionic and nonionic surfactant solutions.

    Science.gov (United States)

    Zhang, Chunlong; Zheng, Gang; Nichols, Courtney M

    2006-01-01

    Micellar partitioning of volatile chlorinated hydrocarbons in surfactant solutions and its effects on vapor-liquid equilibrium is fundamental to the overall design and implementation of surfactant-enhanced aquifer remediation. Surfactant micelles greatly enhance contaminant recovery from the subsurface; however, the reduced volatility of organic compounds compromises the aboveground treatment of surfactant-laden wastewaters using air-stripping process. Batch equilibrium tests were performed to acquire micellar partition coefficients (Km) and apparent Henry's law constants (H*) of three prominent groundwater contaminants (tetrachloroethylene, trichloroethylene, cis-dichlorethylene) in the presence of two anionic surfactants (sodium dodecyl sulfate, SDS; sodium dodecylbenzene sulfonate, SDBS) and two nonionic surfactants (Triton X-100 and Tween 80). The H* values were significantly reduced in the presence of all four surfactants over their critical micelle concentrations (cmc's). On a cmc basis, the anionic surfactant SDS had the greatest effect on H*, followed by SDBS, Triton X-100, and Tween 80. Anionic surfactants decreased H* to an order of magnitude lower than nonionic surfactants, although nonionic surfactants decreased the H* at concentrations significantly lower than the anionic surfactants due to their lower cmc's. Nonionic surfactants present higher Km and molar solubilization ratio than anionic surfactants. Tetrachloroethylene has the highest Km values among three chlorinated solvents, which agrees well with the hydrophobicity (Kow) of these chemicals. An empirical correlation between log Km and log Kow is developed on the basis of data from this study and the Km values reported for a number of chlorinated and nonchlorinated hydrocarbons. Equilibrium data were also tested against three sets of models that describe the partitioning of volatile compounds in vapor-water-micelle phases. Applications of these models in experimentally determining Km from batch

  12. Solvent

    OpenAIRE

    Hamida Y. Mostafa; Ebaa A. El-Shamy; Amal S. Farag; Nadia G. Kandile

    2013-01-01

    Neat ethylacetoacetate (EAA) and its mixtures with a co-solvent and an anti-solvent have been studied for refining of heavy wax distillate fraction to produce substantially non-carcinogenic base oil. The co-solvent and anti-solvent used are dipropylene glycol (DPG) and ethylene glycol (EG) respectively. The solubility characteristics of the main solvent and its mixed solvent systems were studied. Selection of the optimum solvent mixture and extraction variables has been studied. The effect of...

  13. Solvent

    Directory of Open Access Journals (Sweden)

    Hamida Y. Mostafa

    2013-12-01

    Full Text Available Neat ethylacetoacetate (EAA and its mixtures with a co-solvent and an anti-solvent have been studied for refining of heavy wax distillate fraction to produce substantially non-carcinogenic base oil. The co-solvent and anti-solvent used are dipropylene glycol (DPG and ethylene glycol (EG respectively. The solubility characteristics of the main solvent and its mixed solvent systems were studied. Selection of the optimum solvent mixture and extraction variables has been studied. The effect of co-solvent and anti-solvent addition on the carcinogenic potential and raffinate quality has been determined under clearly comparable conditions.

  14. Influence of the ammonium salt anion on the synergistic solvent extraction of lanthanides with mixtures of thenoyltrifluoroacetone and tridecylamine

    Energy Technology Data Exchange (ETDEWEB)

    Dukov, I.L.; Jordanov, V.M. [Univ. of Chemical Technology and Metallurgy, Sofia (Bulgaria). Dept. of Inorganic Chemistry

    1998-08-01

    The synergistic solvent extraction of Pr, Gd and Yb with mixtures of thenoyltrifluoroacetone (HTTA) and primary ammonium salt (tridecylammonium chloride or perchlorate, TDAH(Cl, ClO{sub 4})) in C{sub 6}H{sub 6} has been studied. The composition of the extracted species have been determined as Ln(TTA){sub 3}TDAHA(A{sup {minus}} = Cl{sup {minus}} or ClO{sub 4}{sup {minus}}). The values of the equilibrium constant K{sub T,S} have been calculated. The influence of the ammonium salt anion on the extraction process has been discussed. The separation factors of the pairs Gd/Pr and Yb/Gd have been determined.

  15. The effect of solvent polarity on wormlike micelles using dipropylene glycol (DPG) as a cosolvent in an anionic/zwitterionic mixed surfactant system.

    Science.gov (United States)

    Jiang, Hanqiu; Beaucage, Gregory; Vogtt, Karsten; Weaver, Michael

    2018-01-01

    The behavior/properties of micellar solutions are governed by Coulombic interactions that are influenced by the polarity of the surfactant head groups, hydrophobic tails, and solvent molecules. The addition of co-solvent should have a direct impact on solvent polarity and the size of the micelles are expected to decrease accordingly. In this study, a mixed surfactant system is studied composed of a common anionic surfactant, sodium laureth sulfate-1, modified by a zwitterionic surfactant, cocamidopropyl betaine in deuterated water. In this system, worm-like micelles (WLMs) are formed. The influence of a co-solvent, dipropylene glycol (DPG) in the present of high salt content, is investigated. DPG primarily modifies the dielectric constant of the solvent. It was found that the addition of DPG slightly decreased the micelle radius, but dramatically reduced the persistence length as well as the contour length of the micelles. The relative dependence of contour length on salt concentration is not significantly changed. Thus, it is shown that the self-assembled structure can be tuned by adjusting solvent polarity without affecting the relative tunability of the WLM/ellipsoidal structure through counter ion concentration. Copyright © 2017 Elsevier Inc. All rights reserved.

  16. Overview of the effect of salts on biphasic ionic liquid/water solvent extraction systems: anion exchange, mutual solubility, and thermomorphic properties.

    Science.gov (United States)

    Dupont, David; Depuydt, Daphne; Binnemans, Koen

    2015-06-04

    Hydrophobic (water-immiscible) ionic liquids (ILs) are frequently used as organic phase in solvent extraction studies. These biphasic IL/water extraction systems often also contain metal salts or mineral acids, which can significantly affect the IL trough (un)wanted anion exchange and changes in the solubility of IL in the aqueous phase. In the case of thermomorphic systems, variations in the cloud point temperature are also observed. All these effects have important repercussions on the choice of IL, suitable for a certain extraction system. In this paper, a complete overview of the implications of metal salts on biphasic IL/water systems is given. Using the Hofmeister series as a starting point, a range of intuitive prediction models are introduced, supported by experimental evidence for several hydrophobic ILs, relevant to solvent extraction. Particular emphasis is placed on the IL betainium bis(trifluoromethylsulfonyl)imide [Hbet][Tf2N]. The aim of this work is to provide a comprehensive interpretation of the observed effects of metal salts, so that it can be used to predict the effect on any given biphasic IL/water system instead of relying on case-by-case reports. These prediction tools for the impact of metal salts can be useful to optimize IL synthesis procedures, extraction systems and thermomorphic properties. Some new insights are also provided for the rational design of ILs with UCST or LCST behavior based on the choice of IL anion.

  17. Dynamic equilibria in solvent-mediated anion, cation and ligand exchange in transition-metal coordination polymers: solid-state transfer or recrystallisation?

    Science.gov (United States)

    Cui, Xianjin; Khlobystov, Andrei N; Chen, Xinyong; Marsh, Dan H; Blake, Alexander J; Lewis, William; Champness, Neil R; Roberts, Clive J; Schröder, Martin

    2009-09-07

    The solution properties of a series of transition-metal-ligand coordination polymers [ML(X)(n)](infinity) [M=Ag(I), Zn(II), Hg(II) and Cd(II); L=4,4'-bipyridine (4,4'-bipy), pyrazine (pyz), 3,4'-bipyridine (3,4'-bipy), 4-(10-(pyridin-4-yl)anthracen-9-yl)pyridine (anbp); X=NO(3) (-), CH(3)COO(-), CF(3)SO(3) (-), Cl(-), BF(4) (-); n=1 or 2] in the presence of competing anions, metal cations and ligands have been investigated systematically. Providing that the solubility of the starting complex is sufficiently high, all the components of the coordination polymer, namely the anion, the cation and the ligand, can be exchanged on contact with a solution phase of a competing component. The solubility of coordination polymers is a key factor in the analysis of their reactivity and this solubility depends strongly on the physical properties of the solvent and on its ability to bind metal cations constituting the backbone of the coordination polymer. The degree of reversibility of these solvent-induced anion-exchange transformations is determined by the ratio of the solubility product constants for the starting and resultant complexes, which in turn depend upon the choice of solvent and the temperature. The extent of anion exchange is controlled effectively by the ratio of the concentrations of incoming ions to outgoing ions in the liquid phase and the solvation of various constituent components comprising the coordination polymer. These observations can be rationalised in terms of a dynamic equilibrium of ion exchange reactions coupled with Ostwald ripening of crystalline products. The single-crystal X-ray structures of [Ag(pyz)ClO(4)](infinity) (1), {[Ag(4,4'-bipy)(CF(3)SO(3))]CH(3)CN}(infinity) (2), {[Ag(4,4'-bipy)(CH(3)CN)]ClO(4) 0.5 CH(3)CN}(infinity) (3), metal-free anbp (4), [Ag(anbp)NO(3)(H(2)O)](infinity) (5), {[Cd(4,4'-bipy)(2)(H(2)O)(2)](NO(3))(2)4 H(2)O}(infinity) (6) and {[Zn(4,4'-bipy)SO(4)(H(2)O)(3)] 2 H(2)O}(infinity) (7) are reported.

  18. Symmetry and dynamics of FHF-anion in vacuum, in CD2Cl2and in CCl4. Ab initio MD study of fluctuating solvent-solute hydrogen and halogen bonds.

    Science.gov (United States)

    Pylaeva, S A; Elgabarty, H; Sebastiani, D; Tolstoy, P M

    2017-10-04

    FHF - anion is a classic example of a central-symmetric strongly hydrogen bonded system that has been intensively investigated both experimentally and theoretically. In this paper we focus on solvent effects on symmetry, structure and dynamics of the anion. The FHF - anion is studied in vacuum, dissolved in CH 2 Cl 2 and dissolved in CCl 4 by ab initio molecular dynamics simulations. We show that CH 2 Cl 2 molecules form CHF hydrogen bonds with lone pairs of fluorine atoms, while CCl 4 molecules form halogen bonds. These specific non-covalent solvent-solute interactions are cooperatively coupled to the FHF - hydrogen bonds. The fluctuation of solvent molecules' positions is the driving force changing the FHF - hydrogen bond geometry. Most of the time, the anion is solvated asymmetrically, which leads to the asymmetric bridging particle position, though the time-averaged D ∞h symmetry is retained. Interestingly, this transient asymmetrization of FHF - is more pronounced in CCl 4 , than in CH 2 Cl 2 . We show that the 1 H and 19 F NMR chemicals shifts react sensitively to the changes of anion's geometry and the limiting chemical shifts of free solvated FH and F - are strongly solvent-dependent.

  19. Influence of the amine salt anion on the synergic solvent extraction of praseodymium with mixtures of chelating extractants and tridodecylamine

    Energy Technology Data Exchange (ETDEWEB)

    Dukov, I.L.; Jordanov, V.M. [Higher Inst. of Chemical Technology, Sofia (Bulgaria)

    1995-11-01

    The solvent extraction of Pr with thenoyltrifluoroacetone, (HTTA) or 1-phenyl-3-methyl-4-benzoyl-pyrazol-5-one(HP) and tridodecylammonium salt (TDAHA,A{sup -} = Cl{sup -},NO{sub 3}{sup -}, ClO{sub 4}{sup -}) in C{sub 6}H{sub 6} has been studied. The composition of the extracted species has been determined as Pr(TTA){sub 3} TDAHA and TDAH{sup +}[PrP{sub 4}]{sup -}. The values of the equilibrium constants, have been calculated. The extraction mechanism has been discussed on the basis of the experimental data. 34 refs., 6 figs., 2 tabs.

  20. Lanthanide metal-organic frameworks as multifunctional luminescent sensor for detecting cations, anions and organic solvent molecules in aqueous solution

    Science.gov (United States)

    Liu, Feng; Gao, Wei; Li, Peng; Zhang, Xiu-Mei; Liu, Jie-Ping

    2017-09-01

    A series of water-stable isostructural mono/bimetallic lanthanide metal-organic frameworks (Ln-MOFs) {[Eu5xTb5(1-x)(OH)6(TZI)3(DMA)1.5(H2O)10.5]·DMA·0.5H2O}n (x = 1.0 (1), 0.5 (3), 0.4 (4), 0.3 (5), 0.2 (6), 0.1 (7), 0.05 (8), 0 (2), H3TZI = 5-(1H-tetrazol-5-yl)isophthalic acid) were synthesized. These Ln-MOFs exhibit 3D frameworks in which 1D chains based on pentanuclear [Ln5(μ3-OH)6(COO)5]4+ clusters are linked by TZI backbones. The luminescent investigations revealed that compounds 1 and 2 not only exhibit characteristic Eu3+ and Tb3+ emissions in the red and green regions, respectively, but also can sensitively and selectively detect Fe3+ cations, CO32-, PO43-, AsO43- anions and acetone molecules in aqueous solution. In addition, the luminescent colors of the bimetallic (Tb5(1-x):Eu5x) compounds can easily be tuned by doping isostructural Ln- MOFs with Eu3+ and Tb3+ ions. This work presents some good candidate materials for the potential multifunctional sensors. Eight water-stable isostructural 3D Ln-MOFs {[Eu5xTb5(1-x)(OH)6(TZI)3(DMA)1.5(H2O)10.5]·DMA·0.5H2O}n based on pentanuclear clusters were prepared. The Ln-MOFs represented the rapid and drastic emission quenching induced by Fe3+ cations, CO32-, PO43-, AsO43- anions and acetone molecules in aqueous solution. the luminescence colors of the bimetallic (Tb5(1-x):Eu5x) compounds can easily be tuned by doping isostructural Ln-MOFs with Eu3+ and Tb3+ ions.

  1. Retention prediction of low molecular weight anions in ion chromatography based on quantitative structure-retention relationships applied to the linear solvent strength model.

    Science.gov (United States)

    Park, Soo Hyun; Haddad, Paul R; Talebi, Mohammad; Tyteca, Eva; Amos, Ruth I J; Szucs, Roman; Dolan, John W; Pohl, Christopher A

    2017-02-24

    Quantitative Structure-Retention Relationships (QSRRs) represent a popular technique to predict the retention times of analytes, based on molecular descriptors encoding the chemical structures of the analytes. The linear solvent strength (LSS) model relating the retention factor, k to the eluent concentration (log k=a-blog [eluent]), is a well-known and accurate retention model in ion chromatography (IC). In this work, QSRRs for inorganic and small organic anions were used to predict the regression parameters a and b in the LSS model (and hence retention times) for these analytes under a wide range of eluent conditions, based solely on their chemical structures. This approach was performed on retention data of inorganic and small organic anions from the "Virtual Column" software (Thermo Fisher Scientific). These retention data were recalibrated via a "porting" methodology on three columns (AS20, AS19, and AS11HC), prior to the QSRR modeling. This provided retention data more applicable on recently produced columns which may exhibit changes of column behavior due to batch-to-batch variability. Molecular descriptors for the analytes were calculated with Dragon software using the geometry-optimized molecular structures, employing the AM1 semi-empirical method. An optimal subset of molecular descriptors was then selected using an evolutionary algorithm (EA). Finally, the QSRR models were generated by multiple linear regression (MLR). As a result, six QSRR models with good predictive performance were successfully derived for a- and b-values on three columns (R(2)>0.98 and RMSE0.7 and RMSEP<0.4). Moreover, it was demonstrated that the obtained QSRR models for the a- and b-values can predict the retention times for new analytes with good accuracy and predictability (R(2) of 0.98, RMSE of 0.89min, Qext(F3)(2) of 0.96 and RMSEP of 1.18min). Copyright © 2016 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

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

    2013-05-22

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

  3. 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.

  4. Kinetics of carrier-mediated alkali cation transport through supported liquid membranes: Effect of membrane solvent, co-transported anion, and support

    NARCIS (Netherlands)

    Visser, H.C.; Visser, Herman C.; de Jong, Feike; Reinhoudt, David

    1995-01-01

    The rate-limiting step in the transport of alkali cations through supported liquid membranes mediated by calix [4] arene carriers can be the diffusion of the carrier cation complex through the membrane and/or the kinetics of cation release from the complex. The effects of membrane solvent,

  5. Dependence of the mechanism and regularities of energy transfer in binuclear lanthanide complexes in solutions on the nature of the anion and solvent

    Science.gov (United States)

    Sveshnikova, E. B.; Dudar', S. S.; Lanin, V. E.; Ermolaev, V. L.

    2002-10-01

    The effect of anions contained in solutions on the energy transfer from Tb(III) and Dy(III) ions to different Ln(III) ions is investigated in aqueous and alcohol solutions. It is shown that the regularities revealed in the energy transfer are completely determined by the ratio between the dissociation rate of the binuclear complex and the rate of energy transfer in it. The rate constant k t of energy transfer in solutions in which labile binuclear complexes of Ln(III) ions are linked through the strong acid anions Cl-, NO{3/-}, and HSO{4/-} depends on the nature of ions in the pairs. It is demonstrated that the energy transfer in all the systems predominantly occurs through the induction-resonance mechanism. The rate constants k t in aqueous solutions of weak (acetic, salicylic, and carbonic) acids also depend on the nature of ions interacting in pairs but do not correlate with the Förster overlap integral of the spectra. In labile binuclear complexes, the interaction between these ions proceeds by the exchange-resonance mechanism at a distance of ≈0.4 nm. It is established that the constants k t in alcohol solutions of Ln(III) ions are virtually independent of the nature of the pairs of the ions interacting through the acetate bridge. A comparison of the dissociation rate constants for Ln-anion complexes in alcohol solutions and the expected intracomplex rates of energy transfer in the binuclear complexes offers a satisfactory explanation of the obtained results and makes it possible to determine the association constants for binuclear lanthanide complexes in these solutions.

  6. Water-induced quenching of salicylic anion fluorescence

    NARCIS (Netherlands)

    Joshi, H.C.; Gooijer, C.; van der Zwan, G.

    2002-01-01

    Salicylic anion absorption and emission are studied in a variety of solvents and solvent mixtures. The large Stokes shift observed for this anion is taken to be indicative of a rapid excited state proton transfer reaction to its keto form. The changes in the Stokes shift in the various solvents can

  7. Capability of parasulfonato calix[6]arene, as an anion dopant, and organic solvents in enhancing the sensitivity and loading of glucose oxidase (GOx) on polypyrrole film in a biosensor: a comparative study.

    Science.gov (United States)

    Safarnavadeh, Vahideh; Zare, Karim; Fakhari, Ali Reza

    2013-11-15

    In this study, the effects of two solvents (acetonitrile and water) and an anion dopant (para sulfonato calix[6]arene ((C[6]S)(-6))), on the manufacturing and properties of a polypyrrole (Ppy)-based, glucose oxidase amperometric biosensor were studied. Pyrrole was polymerized using galvanostatic mode in two different solvents, and the effect of (C[6]S)(-6) was studied in aqueous solution. The morphology of the obtained polypyrrole films was studied by scanning electron microscopy (SEM). Glucose oxidase (GOx) was adsorbed on the Ppy films via cross-linking method. Then the amperometric responses of the Pt/Ppy/GOx electrodes were measured using the amperometric method at the potential of 0.7 V in steps of adding a glucose solution to a potassium phosphate buffer. We found that acetonitrile and (C[6]S)(-6) increase the sensitivity of the enzyme electrode up to 79.30 µA M(-1)cm(-2) in comparison with 31.60 μA M(-1)cm(-2) for the electrode synthesized in calixarene free aqueous solvent. Also (C[6]S)(-6) has the main role in preventing leaching the enzyme from the electrode. This fact increases loading of the enzyme and stability of the biosensor. So that the steady state current density of the aforementioned electrode increases linearly with increasing glucose concentration up to 190 mM. Whereas the linearity was observed up to 61 mM and 80 mM for the electrodes made using calixarene free acetonitrile and aqueous solutions, respectively. Copyright © 2013 Elsevier B.V. All rights reserved.

  8. anion dependence

    Indian Academy of Sciences (India)

    SUMAN Das

    the lifetime distributions show a pronounced anion dependence and suggest cluster stability time up to a few nanoseconds. Keywords. Amide deep eutectics; simulations; cluster size and lifetime distributions; anion dependence. 1. Introduction ... industrial applications.11–15 In chemical industry, they are used as ...

  9. Solvents and solvent effects in organic chemistry

    National Research Council Canada - National Science Library

    Reichardt, C; Welton, T

    2011-01-01

    ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Solute-Solvent Interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Solutions...

  10. SOLVENT EXTRACTION PROCESS

    Science.gov (United States)

    Jonke, A.A.

    1957-10-01

    In improved solvent extraction process is described for the extraction of metal values from highly dilute aqueous solutions. The process comprises contacting an aqueous solution with an organic substantially water-immiscible solvent, whereby metal values are taken up by a solvent extract phase; scrubbing the solvent extract phase with an aqueous scrubbing solution; separating an aqueous solution from the scrubbed solvent extract phase; and contacting the scrubbed solvent phase with an aqueous medium whereby the extracted metal values are removed from the solvent phase and taken up by said medium to form a strip solution containing said metal values, the aqueous scrubbing solution being a mixture of strip solution and an aqueous solution which contains mineral acids anions and is free of the metal values. The process is particularly effective for purifying uranium, where one starts with impure aqueous uranyl nitrate, extracts with tributyl phosphate dissolved in carbon tetrachloride, scrubs with aqueous nitric acid and employs water to strip the uranium from the scrubbed organic phase.

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

    Science.gov (United States)

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

    2014-07-15

    A new Schiff base compound, 5-(dimethylamino)-N'-(2-hydroxybenzylidene)naphthalene-1-sulfonohydrazide (R), has been synthesized, characterized, and employed as a selective fluorescence receptor for the recognition of sulfate anions. UV-vis absorption, fluorescence emission, (1)H NMR spectra and DFT calculation studies on the system have been carried out to determine the nature of the interactions between R and anions. The results reveal that the deprotonation of the phenol without the need of a strong base leads to the formation of a hydrogen-bonding complex with a -SO2-NH- group, which is responsible for the spectra changes. The deprotonation process for the selectivity recognition of sulfate can be tuned by the Brønsted-Lowry acid-base reaction in nonaqueous solutions, revealing that suitable phenolic hydroxyl acidity is the key factor for anion recognition selectivity. Copyright © 2014 Elsevier B.V. All rights reserved.

  12. A simple halide-to-anion exchange method for heteroaromatic salts and ionic liquids.

    Science.gov (United States)

    Alcalde, Ermitas; Dinarès, Immaculada; Ibáñez, Anna; Mesquida, Neus

    2012-04-02

    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 CH(3)OH, CH(3)CN and the dipolar nonhydroxylic solvent mixture CH(3)CN:CH(2)Cl(2) (3:7) and the anion exchange was equally successful with both lipophilic cations and anions.

  13. 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.

  14. High mobility and quantum well transistors design and TCAD simulation

    CERN Document Server

    Hellings, Geert

    2013-01-01

    For many decades, the semiconductor industry has miniaturized transistors, delivering increased computing power to consumers at decreased cost. However, mere transistor downsizing does no longer provide the same improvements. One interesting option to further improve transistor characteristics is to use high mobility materials such as germanium and III-V materials. However, transistors have to be redesigned in order to fully benefit from these alternative materials. High Mobility and Quantum Well Transistors: Design and TCAD Simulation investigates planar bulk Germanium pFET technology in chapters 2-4, focusing on both the fabrication of such a technology and on the process and electrical TCAD simulation. Furthermore, this book shows that Quantum Well based transistors can leverage the benefits of these alternative materials, since they confine the charge carriers to the high-mobility material using a heterostructure. The design and fabrication of one particular transistor structure - the SiGe Implant-Free Qu...

  15. High mobility polymer gated organic field effect transistor using zinc ...

    Indian Academy of Sciences (India)

    Mater. Sci., Vol. 37, No. 1, February 2014, pp. 95–99. c Indian Academy of Sciences. High mobility polymer gated organic field effect transistor using zinc phthalocyanine. K R RAJESH. ∗. , V KANNAN, M R KIM, Y S CHAE and J K RHEE. Millimeter- Wave Innovation Technology Research Centre (MINT), Dongguk University,.

  16. High mobility polymer gated organic field effect transistor using zinc ...

    Indian Academy of Sciences (India)

    Home; Journals; Bulletin of Materials Science; Volume 37; Issue 1. High mobility polymer gated organic field effect transistor using zinc ... fabricated using evaporated zinc phthalocyanine as the active layer. Parylene film prepared by chemical vapour deposition was used as the organic gate insulator. The annealing of the ...

  17. Dissolution of anionic surfactant mesophases.

    Science.gov (United States)

    Poulos, Andreas S; Jones, Christopher S; Cabral, João T

    2017-08-09

    Linear and circular solvent penetration experiments are used to study the dissolution of anionic SLE3S surfactant mesophases in water. We show that a lamellar (Lα) phase in contact with water will transit through a series of cubic, hexagonal, and micellar phase bands with sharp interfaces identified from their optical textures. In both linear and circular geometries, the kinetics of front propagation and eventual dissolution are well described by diffusive penetration of water, and a simple model applies to both geometries, with a different effective diffusion coefficient for water Df as the only fitting parameter. Finally, we show a surprising variation of dissolution rates with initial surfactant concentration that can be well explained by assuming that the driving force for solvent penetration is the osmotic pressure difference between neat water and the aqueous fraction of the mesophase that is highly concentrated in surfactant counterions.

  18. A map of high-mobility molecular semiconductors

    Science.gov (United States)

    Fratini, S.; Ciuchi, S.; Mayou, D.; de Laissardière, G. Trambly; Troisi, A.

    2017-10-01

    The charge mobility of molecular semiconductors is limited by the large fluctuation of intermolecular transfer integrals, often referred to as off-diagonal dynamic disorder, which causes transient localization of the carriers' eigenstates. Using a recently developed theoretical framework, we show here that the electronic structure of the molecular crystals determines its sensitivity to intermolecular fluctuations. We build a map of the transient localization lengths of high-mobility molecular semiconductors to identify what patterns of nearest-neighbour transfer integrals in the two-dimensional (2D) high-mobility plane protect the semiconductor from the effect of dynamic disorder and yield larger mobility. Such a map helps rationalizing the transport properties of the whole family of molecular semiconductors and is also used to demonstrate why common textbook approaches fail in describing this important class of materials. These results can be used to rapidly screen many compounds and design new ones with optimal transport characteristics.

  19. 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.

  20. Selective anion exchange and tunable luminescent behaviors of metal-organic framework based supramolecular isomers.

    Science.gov (United States)

    Manna, Biplab; Singh, Shweta; Karmakar, Avishek; Desai, Aamod V; Ghosh, Sujit K

    2015-01-05

    Owing to the conformational (cis or trans) flexibility of a N-donor ligand, the combinations of the same and Cd(ClO4)2 under variable solvent templates afforded two supramolecular isomers based on two-dimensional metal-organic frameworks. Both compounds contain weakly coordinating ClO4(-) anions attached to the metal centers. Both frameworks showed facile anion exchange behaviors with various kinds of foreign anions. Moreover, both frameworks showed anion-driven structural dynamism and exhibited the preferential uptake of strongly coordinating anions over others. Anion-regulated modulation in luminescent behaviors was also observed in both cases.

  1. Solvent substitution

    Energy Technology Data Exchange (ETDEWEB)

    1990-01-01

    The DOE Environmental Restoration and Waste Management Office of Technology Development and the Air Force Engineering and Services Center convened the First Annual International Workshop on Solvent Substitution on December 4--7, 1990. The primary objectives of this joint effort were to share information and ideas among attendees in order to enhance the development and implementation of required new technologies for the elimination of pollutants associated with industrial use of hazardous and toxic solvents; and to aid in accelerating collaborative efforts and technology transfer between government and industry for solvent substitution. There were workshop sessions focusing on Alternative Technologies, Alternative Solvents, Recovery/Recycling, Low VOC Materials and Treatment for Environmentally Safe Disposal. The 35 invited papers presented covered a wide range of solvent substitution activities including: hardware and weapons production and maintenance, paint stripping, coating applications, printed circuit boards, metal cleaning, metal finishing, manufacturing, compliance monitoring and process control monitoring. This publication includes the majority of these presentations. In addition, in order to further facilitate information exchange and technology transfer, the US Air Force and DOE solicited additional papers under a general Call for Papers.'' These papers, which underwent review and final selection by a peer review committee, are also included in this combined Proceedings/Compendium. For those involved in handling, using or managing hazardous and toxic solvents, this document should prove to be a valuable resource, providing the most up-to-date information on current technologies and practices in solvent substitution. Individual papers are abstracted separated.

  2. 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.

  3. Novel heterocyclic thiosemicarbazones derivatives as colorimetric and “turn on” fluorescent sensors for fluoride anion sensing employing hydrogen bonding

    Science.gov (United States)

    Ashok Kumar, S. L.; Saravana Kumar, M.; Sreeja, P. B.; Sreekanth, A.

    2013-09-01

    Two novel heterocyclic thiosemicarbazone derivatives have been synthesized, and characterized, by means of spectroscopic and single crystal X-ray diffraction methods. Their chromophoric-fluorogenic response towards anions in competing solvent dimethyl sulfoxide (DMSO) was studied. The receptor shows selective recognition towards fluoride anion. The binding affinity of the receptors with fluoride anion was calculated using UV-visible and fluorescence spectroscopic techniques.

  4. Expression of high mobility group A proteins in oral leukoplakia.

    Science.gov (United States)

    Larsson, Lena; Jäwert, Fredrik; Magnusson, Bengt; Hasséus, Bengt; Kjeller, Göran

    2013-10-01

    Oral leukoplakia (LPL) is considered a potentially malignant disorder in the oral cavity and the gastric tract. High mobility group A (HMGA) proteins are important in the transformation of normal cells into cancer cells, but there is a lack of knowledge on their importance in oral cancer development. The aim of the current project was to investigate HMGA expression in LPLs with different levels of dysplasia. Biopsies were histologically processed to visualize the expression of HMGA1 and HMGA2 using immunohistochemistry. An increase of HMGA1-positive cells correlating to the degree of dysplasia was registered in the epithelium and in the connective tissue. HMGA2 expression was seen in the epithelium and in the connective tissue but with no obvious correlation to the level of dysplasia. This is, to our knowledge, the first study showing the expression of HMGA proteins in healthy and non-healthy oral mucosa.

  5. High mobility solution-processed hybrid light emitting transistors

    Science.gov (United States)

    Walker, Bright; Ullah, Mujeeb; Chae, Gil Jo; Burn, Paul L.; Cho, Shinuk; Kim, Jin Young; Namdas, Ebinazar B.; Seo, Jung Hwa

    2014-11-01

    We report the design, fabrication, and characterization of high-performance, solution-processed hybrid (inorganic-organic) light emitting transistors (HLETs). The devices employ a high-mobility, solution-processed cadmium sulfide layer as the switching and transport layer, with a conjugated polymer Super Yellow as an emissive material in non-planar source/drain transistor geometry. We demonstrate HLETs with electron mobilities of up to 19.5 cm2/V s, current on/off ratios of >107, and external quantum efficiency of 10-2% at 2100 cd/m2. These combined optical and electrical performance exceed those reported to date for HLETs. Furthermore, we provide full analysis of charge injection, charge transport, and recombination mechanism of the HLETs. The high brightness coupled with a high on/off ratio and low-cost solution processing makes this type of hybrid device attractive from a manufacturing perspective.

  6. A general halide-to-anion switch for imidazolium-based ionic liquids and oligocationic systems using anion exchange resins (A- form).

    Science.gov (United States)

    Alcalde, Ermitas; Dinarès, Immaculada; Ibáñez, Anna; Mesquida, Neus

    2011-03-21

    Further studies on the application of an AER (A(-) form) method broadened the anion exchange scope of representative ionic liquids and bis(imidazolium) systems. Depending on the hydrophobicity nature of the targeted imidazolium species and counteranions, different organic solvents were used to swap halides for assorted anions, proceeding in excellent to quantitative yields.

  7. Anion Recognition by Aliphatic Helical Oligoureas.

    Science.gov (United States)

    Diemer, Vincent; Fischer, Lucile; Kauffmann, Brice; Guichard, Gilles

    2016-10-24

    Anion binding properties of neutral helical foldamers consisting of urea type units in their backbone have been investigated. (1) H NMR titration studies in various organic solvents including DMSO suggest that the interaction between aliphatic oligoureas and anions (CH3 COO(-) , H2 PO4(-) , Cl(-) ) is site-specific, as it largely involves the urea NHs located at the terminal end of the helix (positive pole of the helix), which do not participate to the helical intramolecular hydrogen-bonding network. This mode of binding parallels that found in proteins in which anion-binding sites are frequently found at the N-terminus of an α-helix. (1) H NMR studies suggest that the helix of oligoureas remains largely folded upon anion binding, even in the presence of a large excess of the anion. This study points to potentially useful applications of oligourea helices for the selective recognition of small guest molecules. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Anion exchange in ionic liquid mixtures.

    Science.gov (United States)

    Cha, Seoncheol; Kim, Doseok

    2015-11-28

    Advantage of ionic liquids as designer solvents can be maximized by mixing different ionic liquids (ILs) for a possibility of continuous tunability of material properties. The property of these mixed ILs would be determined by their microscopic conformation between cations and anions. The mixtures of two ILs having 1-butyl-3-methylimidaolium cations and different anions were investigated by IR and NMR spectroscopy, utilizing that the vibrational frequencies of the C-H stretching and bending modes of the most acidic proton in the imidazolium ring of the cation and the NMR chemical shift for the corresponding proton were clearly distinct between the ILs having different anions. The IR absorption spectra of the IL mixtures at different concentrations were well-matched to weighted sums of the two spectra of the pure ILs. In contrast, the two distinct peaks in the NMR spectra of the pure ILs coalesced into a single peak, which shifted continuously following the relative portion of two different ILs in the mixture. IR spectroscopy in the optical frequency range seems to take the instantaneous snapshot of the cation-anion interaction, while NMR spectroscopy in the radio-frequency (∼500 MHz) range samples over a much longer timescale, enough for the cation to interact with different anion species in the mixture.

  9. TRUEX process solvent cleanup with solid sorbents

    Energy Technology Data Exchange (ETDEWEB)

    Tse, Pui-Kwan; Reichley-Yinger, L.; Vandegrift, G.F.

    1989-01-01

    Solid sorbents, alumina, silica gel, and Amberlyst A-26 have been tested for the cleanup of degraded TRUEX-NPH solvent. A sodium carbonate scrub alone does not completely remove acidic degradation products from highly degraded solvent and cannot restore the stripping performance of the solvent. By following the carbonate scrub with either neutral alumina or Amberlyst A-26 anion exchange resin, the performance of the TRUEX-NPH is substantially restored. The degraded TRUEX-NPH was characterized before and after treatment by supercritical fluid chromatography. Its performance was evaluated by americium distribution ratios, phase-separation times, and lauric acid distribution coefficients. 17 refs., 2 figs., 5 tabs.

  10. 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.

  11. Gating of high-mobility InAs metamorphic heterostructures

    Energy Technology Data Exchange (ETDEWEB)

    Shabani, J. [California NanoSystems Institute, University of California, Santa Barbara, California 93106 (United States); McFadden, A. P. [Department of Electrical Engineering, University of California, Santa Barbara, California 93106 (United States); Shojaei, B. [Materials Department, University of California, Santa Barbara, California 93106 (United States); Palmstrøm, C. J. [California NanoSystems Institute, University of California, Santa Barbara, California 93106 (United States); Department of Electrical Engineering, University of California, Santa Barbara, California 93106 (United States); Materials Department, University of California, Santa Barbara, California 93106 (United States)

    2014-12-29

    We investigate the performance of gate-defined devices fabricated on high mobility InAs metamorphic heterostructures. We find that heterostructures capped with In{sub 0.75}Ga{sub 0.25}As often show signs of parallel conduction due to proximity of their surface Fermi level to the conduction band minimum. Here, we introduce a technique that can be used to estimate the density of this surface charge that involves cool-downs from room temperature under gate bias. We have been able to remove the parallel conduction under high positive bias, but achieving full depletion has proven difficult. We find that by using In{sub 0.75}Al{sub 0.25}As as the barrier without an In{sub 0.75}Ga{sub 0.25}As capping, a drastic reduction in parallel conduction can be achieved. Our studies show that this does not change the transport properties of the quantum well significantly. We achieved full depletion in InAlAs capped heterostructures with non-hysteretic gating response suitable for fabrication of gate-defined mesoscopic devices.

  12. High mobility, printable, and solution-processed graphene electronics.

    Science.gov (United States)

    Wang, Shuai; Ang, Priscilla Kailian; Wang, Ziqian; Tang, Ai Ling Lena; Thong, John T L; Loh, Kian Ping

    2010-01-01

    The ability to print graphene sheets onto large scale, flexible substrates holds promise for large scale, transparent electronics on flexible substrates. Solution processable graphene sheets derived from graphite can form stable dispersions in solutions and are amenable to bulk scale processing and ink jet printing. However, the electrical conductivity and carrier mobilities of this material are usually reported to be orders of magnitude poorer than that of the mechanically cleaved counterpart due to its higher density of defects, which restricts its use in electronics. Here, we show that by optimizing several key factors in processing, we are able to fabricate high mobility graphene films derived from large sized graphene oxide sheets, which paves the way for all-carbon post-CMOS electronics. All-carbon source-drain channel electronics fabricated from such films exhibit significantly improved transport characteristics, with carrier mobilities of 365 cm(2)/(V.s) for hole and 281 cm(2)/(V.s) for electron, measured in air at room temperature. In particular, intrinsic mobility as high as 5000 cm(2)/(V.s) can be obtained from such solution-processed graphene films when ionic screening is applied to nullify the Coulombic scattering by charged impurities.

  13. Receptors for anions

    Energy Technology Data Exchange (ETDEWEB)

    Itsikson, N A; Chupakhin, O N [I. Ya. Postovsky Institute of Organic Synthesis, Urals Branch of the Russian Academy of Sciences, Ekaterinburg (Russian Federation); Morzherin, Yu Yu; Matern, A I [B N Yeltsin Urals State Technical University - UPI (Russian Federation)

    2008-09-30

    The published data on receptors for anions with different geometry are generalised. Special attention is given to the analysis of binding abilities of organic ligands. Structural features of complex-forming agents and their properties are considered.

  14. Anion exchange polymer electrolytes

    Science.gov (United States)

    Kim, Yu Seung; Kim, Dae Sik

    2015-06-02

    Anion exchange polymer electrolytes that include guanidinium functionalized polymers may be used as membranes and binders for electrocatalysts in preparation of anodes for electrochemical cells such as solid alkaline fuel cells.

  15. Designation and Exploration of Halide-Anion Recognition Based on Cooperative Noncovalent Interactions Including Hydrogen Bonds and Anion-π.

    Science.gov (United States)

    Liu, Yan-Zhi; Yuan, Kun; Lv, Ling-Ling; Zhu, Yuan-Cheng; Yuan, Zhao

    2015-06-04

    A novel urea-based anion receptor with an electron-deficient aromatic structural unit, N-p-nitrophenyl-N-(4-vinyl-2-five-fluoro-benzoic acid benzyl ester)-phenyl-urea (FUR), was designed to probe the potential for halide-anion recognition through the cooperation of two distinct noncovalent interactions including hydrogen bonds and anion-π in this work. The nature of the recognition interactions between halide-anion and the designed receptor was theoretically investigated at the molecular level. The geometric features of the hydrogen bond and anion-π of the FUR@X(-) (X = F, Cl, Br, and I) systems were thoroughly investigated. The binding energies and thermodynamic information on the halide-anion recognitions show that the presently designed FUR might selectively recognize anion F(-) based on the cooperation of the N-H···F(-) hydrogen bond and anion-π interactions both in vacuum and in solvents. IR and UV-visible spectra of free FUR and FUR@F(-) have been simulated and discussed qualitatively, which may be helpful for further experimental investigations in the future. Additionally, the electronic properties and behaviors of the FUR@X(-) systems were discussed according to the calculations on the natural bond orbital (NBO) data, molecular electrostatic potential (MEP), and weak interaction regions.

  16. 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

  17. Potentiometric anion selective sensors

    NARCIS (Netherlands)

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

    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

  18. Complex anion inclusion compounds: flexible anion-exchange materials.

    Science.gov (United States)

    Williams, Edward R; Leithall, Rebecca M; Raja, Robert; Weller, Mark T

    2013-01-11

    Copper chloropyrophosphate frameworks have been synthesised with a wide variety of complex inorganic anions trapped in a large, flexible, one-dimensional pore, with anions including chloride, bromide, phosphate and the complex metal halo-anions PtCl(4)(2-), PdBr(4)(2-), CuCl(4)(2-) and AuCl(4)(-).

  19. Caustic-Side Solvent Extraction: Chemical and Physical Properties of the Optimized Solvent

    Energy Technology Data Exchange (ETDEWEB)

    Delmau, L.H.

    2002-10-08

    This work was undertaken to optimize the solvent used in the Caustic Side Solvent Extraction (CSSX) process and to measure key chemical and physical properties related to its performance in the removal of cesium from the alkaline high-level salt waste stored in tanks at the Savannah River Site. The need to adjust the solvent composition arose from the prior discovery that the previous baseline solvent was supersaturated with respect to the calixarene extractant. The following solvent-component concentrations in Isopar{reg_sign} L diluent are recommended: 0.007 M calix[4]arene-bis(tert-octylbenzo-crown-6) (BOBCalixC6) extractant, 0.75 M 1-(2,2,3,3-tetrafluoropropoxy)-3-(4-sec-butylphenoxy)-2-propanol (Cs-7SB) phase modifier, and 0.003 M tri-n-octylamine (TOA) stripping aid. Criteria for this selection included BOBCalixC6 solubility, batch cesium distribution ratios (D{sub Cs}), calculated flowsheet robustness, third-phase formation, coalescence rate (dispersion numbers), and solvent density. Although minor compromises within acceptable limits were made in flowsheet robustness and solvent density, significant benefits were gained in lower risk of third-phase formation and lower solvent cost. Data are also reported for the optimized solvent regarding the temperature dependence of D{sub Cs} in extraction, scrubbing, and stripping (ESS); ESS performance on recycle; partitioning of BOBCalixC6, Cs-7SB, and TOA to aqueous process solutions; partitioning of organic anions; distribution of metals; solvent phase separation at low temperatures; solvent stability to elevated temperatures; and solvent density and viscosity. Overall, the technical risk of the CSSX process has been reduced by resolving previously identified issues and raising no new issues.

  20. Degreaser Reduces Solvent Loss

    Science.gov (United States)

    Du Fresne, E. R.

    1985-01-01

    Escape of solvent minimized by second cooling coil. Degreaser suppresses solvent-vapor loss through parts-basket dragout and air drafts. Within C02 blanket, convection repeatedly exposes C02/solvent mixture to cold spot created by C02 coil. Solvent vapor condenses, then runs down via through to cold tank. This small expenditure of C02 minimizes health and environmental hazards.

  1. Compound forming extractants, solvating solvents and inert solvents IUPAC chemical data series

    CERN Document Server

    Marcus, Y; Kertes, A S

    2013-01-01

    Equilibrium Constants of Liquid-Liquid Distribution Reactions, Part III: Compound Forming Extractants, Solvating Solvents, and Inert Solvents focuses on the compilation of equilibrium constants of various compounds, such as acids, ions, salts, and aqueous solutions. The manuscript presents tables that show the distribution reactions of carboxylic and sulfonic acid extractants and their dimerization and other reactions in the organic phase and extraction reactions of metal ions from aqueous solutions. The book also states that the inorganic anions in these solutions are irrelevant, since they d

  2. Fission product solvent extraction

    Energy Technology Data Exchange (ETDEWEB)

    Moyer, B.A.; Bonnesen, P.V.; Sachleben, R.A. [and others

    1998-02-01

    Two main objectives concerning removal of fission products from high-level tank wastes will be accomplished in this project. The first objective entails the development of an acid-side Cs solvent-extraction (SX) process applicable to remediation of the sodium-bearing waste (SBW) and dissolved calcine waste (DCW) at INEEL. The second objective is to develop alkaline-side SX processes for the combined removal of Tc, Cs, and possibly Sr and for individual separation of Tc (alone or together with Sr) and Cs. These alkaline-side processes apply to tank wastes stored at Hanford, Savannah River, and Oak Ridge. This work exploits the useful properties of crown ethers and calixarenes and has shown that such compounds may be economically adapted to practical processing conditions. Potential benefits for both acid- and alkaline-side processing include order-of-magnitude concentration factors, high rejection of bulk sodium and potassium salts, and stripping with dilute (typically 10 mM) nitric acid. These benefits minimize the subsequent burden on the very expensive vitrification and storage of the high-activity waste. In the case of the SRTALK process for Tc extraction as pertechnetate anion from alkaline waste, such benefits have now been proven at the scale of a 12-stage flowsheet tested in 2-cm centrifugal contactors with a Hanford supernatant waste simulant. SRTALK employs a crown ether in a TBP-modified aliphatic kerosene diluent, is economically competitive with other applicable separation processes being considered, and has been successfully tested in batch extraction of actual Hanford double-shell slurry feed (DSSF).

  3. Anion-Directed Metallocages: A Study on the Tendency of Anion Templation.

    Science.gov (United States)

    Wu, Jing-Yun; Zhong, Ming-Shiou; Chiang, Ming-Hsi

    2017-11-13

    Self-assembly of Cu(NO3 )2 ⋅3 H2 O and di(3-pyridylmethyl)amine (dpma) with addition of different acids (HNO3 , HOAc, HCl, HClO4 , HOTf, HPF6 , HBF4 , and H2 SO4 ) afforded a family of anion-templated tetragonal metallocages with a cationic prismatic structure of [(G(n-) )⊂{Cu2 (Hdpma)4 }]((8-n)+) (G(n-) =NO3(-) , PF6(-) , SiF6(2-) ) with different ligating anions/solvents (NO3(-) , Cl(-) , ClO4(-) , OTf(-) , H2 O) outside the cage. Systematic competitive experiments have rationalized the tendency of anion templation towards the formation of metallocages [(G(n-) )⊂{Cu2 (Hdpma)4 }]((8-n)+) as occurring in the order SiF6(2-) ≈PF6(-) >NO3(-) >SO4(2-) ≈ClO4(-) ≈BF4(-) . This sequence is mostly elucidated by shape control over size selectivity and electrostatic attraction between the cationic {Cu2 (Hdpma)4 }(8+) host and the anionic guests. In addition, these results have also roughly ranked the anion coordination ability in the order Cl(-) , ClO4(-) , OTf(-) >NO3(-) >BF4(-) , CH3 SO4(-) . Magnetic studies of metallocages 1 t and 2-4 suggest that the fitted magnetic interaction, being weakly magnetically coupled overall, is interpreted as a result of the combination of intracage ferromagnetic coupling integrals and intercage antiferromagnetic exchange; both contributions are very weak and comparable in strength. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Anion recognition by azophenol thiourea-based chromogenic sensors: a combined DFT and molecular dynamics investigation.

    Science.gov (United States)

    Wong, Ming Wah; Xie, Huifang; Kwa, Soo Tin

    2013-01-01

    The relative binding affinities of several anions towards 2-nitroazophenol thiourea-based receptors were studied using density functional theory (DFT) in the gas phase and in chloroform solvent via PCM calculations. Both receptors have five distinctive NH and OH hydrogen donor atoms. All receptor-anion complexes are characterized by five intermolecular hydrogen bonds. The binding free energies are strongly influenced by a dielectric medium, and the solvation effect alters the trend of anion binding to the receptor. The calculated order of anion binding affinity for the receptor in chloroform, H2PO4->AcO->F->Cl->HSO4->NO3-, is in excellent accord with experimental findings. The overall order of binding affinity is attributed to the basicity of the anion, the effect of solvation, and the number of proton acceptors available. Calculations of the NMR and UV-vis spectra strongly support the experimental characterization of the receptor-anion complexes. Explicit solvent molecular dynamics simulations of selected receptor-anion complexes were also carried out. Analysis of the structural descriptors revealed that the anions were strongly bound within the binding pocket via hydrogen-bonding interactions to the five receptor protons throughout the simulation.

  5. 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.

  6. A Programmable Resilient High-Mobility SDN+NFV Architecture for UAV Telemetry Monitoring

    Science.gov (United States)

    White, Kyle J. S.; Pezaros, Dimitrios P.; Denney, Ewen; Knudson, Matt D.

    2017-01-01

    With the explosive growth in UAV numbers forecast worldwide, a core concern is how to manage the ad-hoc network configuration required for mobility management. As UAVs migrate among ground control stations, associated network services, routing and operational control must also rapidly migrate to ensure a seamless transition. In this paper, we present a novel, lightweight and modular architecture which supports high mobility, resilience and flexibility through the application of SDN and NFV principles on top of the UAV infrastructure. By combining SDN programmability and Network Function Virtualization we can achieve resilient infrastructure migration of network services, such as network monitoring and anomaly detection, coupled with migrating UAVs to enable high mobility management. Our container-based monitoring and anomaly detection Network Functions (NFs) can be tuned to specific UAV models providing operators better insight during live, high-mobility deployments. We evaluate our architecture against telemetry from over 80flights from a scientific research UAV infrastructure.

  7. High-mobility BaSnO3 grown by oxide molecular beam epitaxy

    Directory of Open Access Journals (Sweden)

    Santosh Raghavan

    2016-01-01

    Full Text Available High-mobility perovskite BaSnO3 films are of significant interest as new wide bandgap semiconductors for power electronics, transparent conductors, and as high mobility channels for epitaxial integration with functional perovskites. Despite promising results for single crystals, high-mobility BaSnO3 films have been challenging to grow. Here, we demonstrate a modified oxide molecular beam epitaxy (MBE approach, which supplies pre-oxidized SnOx. This technique addresses issues in the MBE of ternary stannates related to volatile SnO formation and enables growth of epitaxial, stoichiometric BaSnO3. We demonstrate room temperature electron mobilities of 150 cm2 V−1 s−1 in films grown on PrScO3. The results open up a wide range of opportunities for future electronic devices.

  8. High-mobility BaSnO{sub 3} grown by oxide molecular beam epitaxy

    Energy Technology Data Exchange (ETDEWEB)

    Raghavan, Santosh; Schumann, Timo; Kim, Honggyu; Zhang, Jack Y.; Cain, Tyler A.; Stemmer, Susanne, E-mail: stemmer@mrl.ucsb.edu [Materials Department, University of California, Santa Barbara, California 93106-5050 (United States)

    2016-01-01

    High-mobility perovskite BaSnO{sub 3} films are of significant interest as new wide bandgap semiconductors for power electronics, transparent conductors, and as high mobility channels for epitaxial integration with functional perovskites. Despite promising results for single crystals, high-mobility BaSnO{sub 3} films have been challenging to grow. Here, we demonstrate a modified oxide molecular beam epitaxy (MBE) approach, which supplies pre-oxidized SnO{sub x}. This technique addresses issues in the MBE of ternary stannates related to volatile SnO formation and enables growth of epitaxial, stoichiometric BaSnO{sub 3}. We demonstrate room temperature electron mobilities of 150 cm{sup 2} V{sup −1} s{sup −1} in films grown on PrScO{sub 3}. The results open up a wide range of opportunities for future electronic devices.

  9. Radiation induced redox reactions and fragmentation of constituent ions in ionic liquids. I. Anions.

    Energy Technology Data Exchange (ETDEWEB)

    Shkrob, I. A.; Marin, T.; Chemerisov, S.; Wishart, J. (Chemical Sciences and Engineering Division); (BNL); (Benedictine Univ.)

    2011-04-14

    Room temperature ionic liquids (IL) find increasing use for the replacement of organic solvents in practical applications, including their use in solar cells and electrolytes for metal deposition, and as extraction solvents for the reprocessing of spent nuclear fuel. The radiation stability of ILs is an important concern for some of these applications, as previous studies suggested extensive fragmentation of the constituent ions upon irradiation. In the present study, electron paramagnetic resonance (EPR) spectroscopy has been used to identify fragmentation pathways for constituent anions in ammonium, phosphonium, and imidazolium ILs. Many of these detrimental reactions are initiated by radiation-induced redox processes involving these anions. Scission of the oxidized anions is the main fragmentation pathway for the majority of the practically important anions; (internal) proton transfer involving the aliphatic arms of these anions is a competing reaction. For perfluorinated anions, fluoride loss following dissociative electron attachment to the anion can be even more prominent than this oxidative fragmentation. Bond scission in the anion was also observed for NO{sub 3}{sup -} and B(CN){sub 4}{sup -} anions and indirectly implicated for BF{sub 4}{sup -} and PF{sub 6}{sup -} anions. Among small anions, CF{sub 3}SO{sub 3}{sup -} and N(CN){sub 2}{sup -} are the most stable. Among larger anions, the derivatives of benzoate and imide anions were found to be relatively stable. This stability is due to suppression of the oxidative fragmentation. For benzoates, this is a consequence of the extensive sharing of unpaired electron density by the {pi}-system in the corresponding neutral radical; for the imides, this stability could be the consequence of N-N {sigma}{sup 2}{sigma}*{sup 1} bond formation involving the parent anion. While fragmentation does not occur for these 'exceptional' anions, H atom addition and electron attachment are prominent. Among the

  10. NEPTUNIUM SOLVENT EXTRACTION PROCESS

    Science.gov (United States)

    Dawson, L.R.; Fields, P.R.

    1959-10-01

    The separation of neptunium from an aqueous solution by solvent extraction and the extraction of neptunium from the solvent solution are described. Neptunium is separated from an aqueous solution containing tetravalent or hexavalent neptunium nitrate, nitric acid, and a nitrate salting out agent, such as sodium nitrate, by contacting the solution with an organic solvent such as diethyl ether. Subsequently, the neptunium nitrate is extracted from the organic solvent extract phase with water.

  11. The many ways of making anionic clays

    Indian Academy of Sciences (India)

    Unknown

    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 ...

  12. The many ways of making anionic clays

    Indian Academy of Sciences (India)

    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 ...

  13. Autoantibodies to high mobility group box 1 in patients with Incomplete and Systemic Lupus Erythematosus

    NARCIS (Netherlands)

    Schaper, F.; De Leeuw, K.; Horst, G.; Maas, F.; Beijeren, D.V.; Bijzet, J.; Heeringa, P.; Limburg, P.C.; Westra, J.

    2015-01-01

    Introduction. High Mobility Group Box-1 (HMGB1) is involved in the pathogenesis of Systemic Lupus Erythematosus (SLE). However, the role of autoantibodies to HMGB1 is unclear. Therefore levels of anti-HMGB1 and their reactivity to HMGB1 BoxA and BoxB were examined in association with disease

  14. Autoantibodies Against High Mobility Group Box 1 (HMGB1) in Patients with SLE

    NARCIS (Netherlands)

    Schaper, Fleur; Horst, Gerda; Henegouwen, Daan van Beijeren Bergenen; Bijzet, Johan; de Leeuw, Karina; Stel, Alja; Limburg, Pieter C.; Heeringa, Peter; Westra, Johanna

    2014-01-01

    Background/Purpose: High mobility group box 1 (HMGB1) is a damage-associated molecular pattern and can be divided in three separate domains: the A Box, B Box and the acidic tail. Box A by itself serves as a competitive antagonist for HMGB1 and inhibits HMGB1 activity. In an earlier study we showed

  15. Recent Developments in the Role of High-Mobility Group Box 1 in Systemic Lupus Erythematosus

    NARCIS (Netherlands)

    Schaper, Fleur; Westra, Johanna; Bijl, Marc

    2014-01-01

    High-mobility group box 1 (HMGB1) is an important molecule for several nuclear processes. Recently, HMGB1 has gained much attention as a damage-associated molecular pattern (DAMP) and has been implicated in the pathogenesis of several (auto)immune diseases, in particular, systemic lupus

  16. High mobility group A1 enhances tumorigenicity of human cholangiocarcinoma and confers resistance to therapy

    DEFF Research Database (Denmark)

    Quintavalle, Cristina; Burmeister, Katharina; Piscuoglio, Salvatore

    2017-01-01

    High mobility group A1 (HMGA1) protein has been described to play an important role in numerous types of human carcinoma. By the modulation of several target genes HMGA1 promotes proliferation and epithelial-mesenchymal transition of tumor cells. However, its role in cholangiocarcinoma (CCA) has...

  17. Anion-responsive supramolecular gels.

    Science.gov (United States)

    Maeda, Hiromitsu

    2008-01-01

    Supramolecular gels that change their state or structure in response to anion stimuli have been highlighted. Only a few examples exist of such supramolecular gels, the structures and properties of which can be controlled and modulated by interactions with anions. To form anion-responsive dimensionally-controlled organized structures, the constituent low-molecular-weight gelator molecules must act as anion receptors by possessing one or more of van der Waals interaction units (aliphatic chains), stacking pi planes, hydrogen-bonding sites, and metal-coordination units. This Concept focuses on the gelation and transition behaviors of amide- and urea-based anion-stimulated systems, metal-coordinated systems, and novel acyclic pi-conjugated oligopyrroles that act as "molecular flippers."

  18. A theoretical study of ternary indole-cation-anion complexes.

    Science.gov (United States)

    Carrazana-García, Jorge A; Cabaleiro-Lago, Enrique M; Campo-Cacharrón, Alba; Rodríguez-Otero, Jesús

    2014-12-07

    The simultaneous interactions of an anion and a cation with a π system were investigated by MP2 and M06-2X theoretical calculations. Indole was chosen as a model π system for its relevance in biological environments. Two different orientations of the anion, interacting with the N-H and with the C-H groups of indole, were considered. The four cations (Na(+), NH4(+), C(NH2)3(+) and N(CH3)4(+)) and the four anions (Cl(-), NO3(-), HCOO(-) and BF4(-)) included in the study are of biological interest. The total interaction energy of the ternary complexes was calculated and separated into its two- and three-body components and all of them are further divided into their electrostatic, exchange, repulsion, polarization and dispersion contributions using the local molecular orbital-energy decomposition analysis (LMO-EDA) methodology. The binding energy of the indole-cation-anion complexes depends on both ions, with the cation having the strongest effect. The intense cation-anion attraction determines the geometric and energetic features in all ternary complexes. These structures, with both ions on the same side of the π system, show an anti-cooperative interaction. However, the interaction is not only determined by electrostatics, but also the polarization contribution is important. Specific interactions like the one established between the anion and the N-H group of indole or the proton transfer between an acidic cation and a basic anion play a significant role in the energetics and the structure of particular complexes. The presence of the polar solvent as modelled with the polarizable continuum model (PCM) does not seem to have a significant effect on the geometry of the ternary complexes, but drastically weakens the interaction energy. Also, the strength of the interaction is reduced at a faster rate when the anion is pushed away, compared to the results obtained in the gas phase. The combination of PCM with the addition of one water molecule indicates that the PCM

  19. Competitive solvation of (bis)(trifluoromethanesulfonyl)imide anion by acetonitrile and water

    DEFF Research Database (Denmark)

    Chaban, Vitaly

    2014-01-01

    Competitive solvation of an ion by two or more solvents is one of the key phenomena determining the identity of our world. Solvation in polar solvents frequently originates from non-additive non-covalent interactions. Pre-parametrized potentials poorly capture these interactions, unless the force...... and temperature coupling. Using a competitive solvation of (bis)(trifluoromethanesulfonyl)imide anion in acetonitrile and water, the work demonstrates efficiency and robustness of PM7-MD. (C) 2014 Elsevier B.V. All rights reserved....

  20. Anionic and zwitterionic copper(I) complexes incorporating an anionic N-heterocyclic carbene decorated with a malonate backbone: synthesis, structure and catalytic applications.

    Science.gov (United States)

    César, Vincent; Barthes, Cécile; Farré, Yoann C; Cuisiat, Stéphane V; Vacher, Bernard Y; Brousses, Rémy; Lugan, Noël; Lavigne, Guy

    2013-05-28

    The anionic malonate-derived N-heterocyclic carbenes (maloNHCs) react cleanly and rapidly with copper chloride to generate the anionic complexes of type [(maloNHC)CuCl]·Li, which crystallize in the solid state either in an oligomeric trimer arrangement or in polymeric helixes depending on the substitution pattern and the solvent. Ten zwitterionic heteroleptic Cu(I) complexes combining the anionic maloNHC and a neutral imidazol-2-ylidene are also obtained in a very selective manner and fully characterized. Whereas the anionic complexes are relatively active catalysts for the hydrosilylation of carbonyl compounds, the zwitterionic complexes reveal to be efficient and extremely robust pre-catalysts for the intramolecular cyclopropanation reaction of a diazo ester and outperform the corresponding cationic Cu(i) complexes with classical imidazol-2-ylidenes.

  1. 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.

  2. Large yield production of high mobility freely suspended graphene electronic devices on a polydimethylglutarimide based organic polymer

    NARCIS (Netherlands)

    Tombros, Nikolaos; Veligura, Alina; Junesch, Juliane; Berg, J. Jasper van den; Zomer, Paul J.; Wojtaszek, Magdalena; Vera Marun, Ivan J.; Jonkman, Harry T.; Wees, Bart J. van

    2011-01-01

    The recent observation of a fractional quantum Hall effect in high mobility suspended graphene devices introduced a new direction in graphene physics, the field of electron–electron interaction dynamics. However, the technique used currently for the fabrication of such high mobility devices has

  3. Task Phase Recognition for Highly Mobile Workers in Large Building Complexes

    DEFF Research Database (Denmark)

    Stisen, Allan; Mathisen, Andreas; Krogh, Søren

    2016-01-01

    by visualizing coworkers’ task progress, automatic notifications based on context awareness, and record filing of task statuses and completions. This paper presents methods to sense and detect highly mobile workers’ tasks phases in large building complexes. Large building complexes restrict the technologies...... requirements on the accuracy of the indoor positioning, and thus come with low deployment and maintenance effort in real-world settings. We evaluated the proposed methods in a large hospital complex, where the highly mobile workers were recruited among the non-clinical workforce. The evaluation is based...... on manually labelled real-world data collected over 4 days of regular work life of the mobile workforce. The collected data yields 83 tasks in total involving 8 different orderlies from a major university hospital with a building area of 160, 000 m2. The results show that the proposed methods can distinguish...

  4. Anion tuning and polymer templating in a simple low molecular weight organogelator.

    Science.gov (United States)

    Piepenbrock, Marc-Oliver M; Clarke, Nigel; Foster, Jonathan A; Steed, Jonathan W

    2011-02-21

    A simple triethoxysilane appended bis(urea) low molecular weight gelator (LMWG) affords strong gels in organic solvents that are susceptible to fine tuning by anion binding, while the gel structure can be rigidified into a porous hybrid polymer material by hydrolysis of the triethoxysilane end groups.

  5. Hydrogen bond mediated stabilization of the salt bridge structure for the glycine dimer anion

    NARCIS (Netherlands)

    Heiles, S.; Cooper, R.J.; Berden, G.; Oomens, J.; Williams, E.R.

    2015-01-01

    The formation of a salt bridge in deprotonated glycine dimer anions in a solvent-free environment is investigated using both infrared multiple photon dissociation spectroscopy between 600 and 1800 cm(-1) and theory. The zwitterionic and nonzwitterionic forms of glycine in this complex are computed

  6. Emerging Role of High-Mobility Group Box 1 (HMGB1) in Liver Diseases

    OpenAIRE

    Chen, Ruochan; Hou, Wen; Zhang, Qiuhong; Kang, Rui; Fan, Xue-Gong; Tang, Daolin

    2013-01-01

    Damage-associated molecular pattern (DAMP) molecules are essential for the initiation of innate inflammatory responses to infection and injury. The prototypic DAMP molecule, high-mobility group box 1 (HMGB1), is an abundant architectural chromosomal protein that has location-specific biological functions: within the nucleus as a DNA chaperone, within the cytosol to sustain autophagy and outside the cell as a DAMP molecule. Recent research indicates that aberrant activation of HMGB1 signaling ...

  7. Mobility management for highly mobile users and vehicular networks in heterogeneous environments

    OpenAIRE

    Andersson, Karl; Åhlund, Christer; Gukhool, Balkrishna Sharma; Cherkaoui, Soumaya

    2008-01-01

      With the recent developments in wireless networks, different radio access technologies are used in different places depending on capacity in terms of throughput, cell size, scalability etc. In this context, mobile users, and in particular highly mobile users and vehicular networks, will see an increasing number and variety of wireless access points enabling Internet connectivity. Such a heterogeneous networking environment needs, however, an efficient mobility management scheme offering ...

  8. Interaction-induced huge magnetoresistance in a high mobility two-dimensional electron gas

    Energy Technology Data Exchange (ETDEWEB)

    Bockhorn, L.; Haug, R. J. [Institut für Festkörperphysik, Leibniz Universität Hannover, D-30167 Hannover (Germany); Gornyi, I. V. [Institut für Nanotechnologie, Karlsruher Institut of Technology, D-76021 Karlsruhe (Germany); Schuh, D. [Institut für Experimentelle und Angewandte Physik, Universität Regensburg, D-93053 Regensburg (Germany); Wegscheider, W. [ETH Zürich (Switzerland)

    2013-12-04

    A strong negative magnetoresistance is observed in a high-mobility two-dimensional electron gas in a GaAs/Al{sub 0.3}Ga{sub 0.7}As quantum well. We discuss that the negative magnetoresistance consists of a small peak induced by a combination of two types of disorder and a huge magnetoresistance explained by the interaction correction to the conductivity for mixed disorder.

  9. Dietary differentiation and the evolution of population genetic structure in a highly mobile carnivore.

    Directory of Open Access Journals (Sweden)

    Małgorzata Pilot

    Full Text Available Recent studies on highly mobile carnivores revealed cryptic population genetic structures correlated to transitions in habitat types and prey species composition. This led to the hypothesis that natal-habitat-biased dispersal may be responsible for generating population genetic structure. However, direct evidence for the concordant ecological and genetic differentiation between populations of highly mobile mammals is rare. To address this we analyzed stable isotope profiles (δ(13C and δ(15N values for Eastern European wolves (Canis lupus as a quantifiable proxy measure of diet for individuals that had been genotyped in an earlier study (showing cryptic genetic structure, to provide a quantitative assessment of the relationship between individual foraging behavior and genotype. We found a significant correlation between genetic distances and dietary differentiation (explaining 46% of the variation in both the marginal test and crucially, when geographic distance was accounted for as a co-variable. These results, interpreted in the context of other possible mechanisms such as allopatry and isolation by distance, reinforce earlier studies suggesting that diet and associated habitat choice are influencing the structuring of populations in highly mobile carnivores.

  10. Colorimetric determination of pyrophosphate anion and its application to adenylation enzyme assay.

    Science.gov (United States)

    Katano, Hajime; Watanabe, Hiro; Takakuwa, Masahiro; Maruyama, Chitose; Hamano, Yoshimitsu

    2013-01-01

    A colorimetric pyrophosphate assay based on the formation and reduction of the 18-molybdopyrophosphate ([(P2O7)Mo18O54](4-)) anion in an acetonitrile-water mixed solvent was modified and improved. The [(P2O7)Mo18O54](4-) anion is precipitated from the acetonitrile-water solution containing MoO4(2-) and HCl, and is re-dissolved in neat acetonitrile or propylene carbonate. This separation process decreases the interference by ATP, and prevents a yellow coloration of the reducing agent, ascorbic acid, due to excess Mo(VI) species. In the organic solvent, the [(P2O7)Mo18O54](4-) anion is reduced to a more intense blue molybdopyrophosphate species. The application of the colorimetry to the assay of adenylation enzymes is also described in this note.

  11. 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.

  12. 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

  13. SOLVENT EXTRACTION OF NEPTUNIUM

    Science.gov (United States)

    Butler, J.P.

    1958-08-12

    A process is described for the recovery of neptuniunn from dissolver solutions by solvent extraction. The neptunium containing solution should be about 5N, in nitric acid.and about 0.1 M in ferrous ion. The organic extracting agent is tributyl phosphate, and the neptuniunn is recovered from the organic solvent phase by washing with water.

  14. High mobility group box 1/toll-like receptor 4/myeloid differentiation factor 88 signaling promotes progression of gastric cancer.

    Science.gov (United States)

    Yue, Yanqiu; Zhou, Tao; Gao, Yanjing; Zhang, Zongli; Li, Li; Liu, Lin; Shi, Wenna; Su, Lihui; Cheng, Baoquan

    2017-03-01

    High mobility group box 1 and toll-like receptor 4/myeloid differentiation factor 88 signaling pathway have been indicated to have oncogenic effects in many cancers. However, the role of high mobility group box 1/toll-like receptor 4/myeloid differentiation factor 88 signaling pathway in the development of gastric cancer remains unclear. In this study, we demonstrated that high mobility group box 1, toll-like receptor 4, and myeloid differentiation factor 88 were overexpressed in gastric cancer tumors compared with the adjacent non-tumor tissues. The overexpression of high mobility group box 1, toll-like receptor 4, and myeloid differentiation factor 88 were correlated with tumor-node-metastasis stage (p = 0.0068, p = 0.0063, p = 0.0173) and lymph node metastasis (p = 0.0272, p = 0.0382, and p = 0.0495). Furthermore, we observed that knockdown of high mobility group box 1 by high mobility group box 1-small interfering RNA suppressed the expression of toll-like receptor 4 and myeloid differentiation factor 88. Blockage of high mobility group box 1/toll-like receptor 4/myeloid differentiation factor 88 signaling by high mobility group box 1-small interfering RNA resulted in elevation of apoptotic ratio and inhibition of cell growth, migration, and invasion by upregulating Bax expression and downregulating Bcl-2, matrix metalloproteinase-2, nuclear factor kappa B/p65 expression, and the nuclear translocation of nuclear factor kappa B/p65 in gastric cancer cells. Our findings suggest that high mobility group box 1/toll-like receptor 4/myeloid differentiation factor 88 signaling pathway may contribute to the development and progression of gastric cancer via the nuclear factor kappa B pathway and it also represents a novel potential therapeutic target for gastric cancer.

  15. Ion and solvent Transport in Polypyrrole: Experimental Test of Osmotic Model

    DEFF Research Database (Denmark)

    Velmurugu, Yogambigai; Skaarup, Steen

    2005-01-01

    Ion and solvent transport in the conjugated polymer actuator material, polypyrrole, doped with the immobile anion dodecyl benzene sulphonate, has been investigated by simultaneous cyclic voltammetry and Electrochemical Quartz Crystal Microbalance measurements. The purpose was to elucidate the pre...... from almost pure cation transport to ca. equal amount of anion transport; exchanging Br- for Cl- ions has only negligible effect at lower concentrations at equal osmotic pressures. Ca. 4 H2O molecules are tightly bound to each Na+ ion at concentrations

  16. 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.

  17. Conductance fluctuations in high mobility monolayer graphene: Nonergodicity, lack of determinism and chaotic behavior.

    Science.gov (United States)

    da Cunha, C R; Mineharu, M; Matsunaga, M; Matsumoto, N; Chuang, C; Ochiai, Y; Kim, G-H; Watanabe, K; Taniguchi, T; Ferry, D K; Aoki, N

    2016-09-09

    We have fabricated a high mobility device, composed of a monolayer graphene flake sandwiched between two sheets of hexagonal boron nitride. Conductance fluctuations as functions of a back gate voltage and magnetic field were obtained to check for ergodicity. Non-linear dynamics concepts were used to study the nature of these fluctuations. The distribution of eigenvalues was estimated from the conductance fluctuations with Gaussian kernels and it indicates that the carrier motion is chaotic at low temperatures. We argue that a two-phase dynamical fluid model best describes the transport in this system and can be used to explain the violation of the so-called ergodic hypothesis found in graphene.

  18. Photovoltaic infrared photoresponse of the high-mobility graphene quantum Hall system due to cyclotron resonance

    Science.gov (United States)

    Masubuchi, Satoru; Onuki, Masahiro; Arai, Miho; Yamaguchi, Takehiro; Watanabe, Kenji; Taniguchi, Takashi; Machida, Tomoki

    2013-09-01

    We report on the infrared photoresponse of high-mobility graphene in high magnetic fields. Two types of photoresponse signals were observed that were due to photovoltaic and bolometric effects. The photovoltaic signal was observed in the quantum Hall regime, whereas the bolometric signal was dominant in the quantum Hall transition regime. The photovoltaic effect, which was induced by cyclotron resonance, was observable up to 180 K. The polarity of the photovoltaic photoresponse was shown to be systematically reversed on reversal of the applied magnetic field direction and measurement geometry, suggesting that the photovoltage signals were generated along the quantum Hall edge channel.

  19. SOLVENT EXTRACTION OF RUTHENIUM

    Science.gov (United States)

    Hyman, H.H.; Leader, G.R.

    1959-07-14

    The separation of rathenium from aqueous solutions by solvent extraction is described. According to the invention, a nitrite selected from the group consisting of alkali nitrite and alkaline earth nitrite in an equimolecular quantity with regard to the quantity of rathenium present is added to an aqueous solution containing ruthenium tetrantrate to form a ruthenium complex. Adding an organic solvent such as ethyl ether to the resulting mixture selectively extracts the rathenium complex.

  20. Application of Multivariate Analysis in Understanding Anions in Soils Close to an Abandoned Manganese Oxide Ore Mine

    Science.gov (United States)

    Ekosse, Georges-Ivo E.

    Multivariate Analysis (MVA) was used in elucidating on the relationships and environmental implications of anions (particularly chloride, sulphate and carbonate which generally affect bioavailability of soil nutrients) in soils within the proximity of an abandoned Mn oxide ore mine in Southeastern Botswana. Four hundred soil samples were obtained from a 4 km2 area close to the abandoned mine and analysed for their anionic contents and pH. The Statistical Package for Social Sciences (SPSS) software was used for data processing. Anion concentrations in the soil samples were: chloride = 0.2 to 11.9 mg kg-1, with a mean of 7.63 mg kg-1, sulphate = 2.1 to 47.5 mg kg-1, with a mean of 19.36 mg kg-1 and carbonate = 5.1 g kg-1 to 59.1 g kg-1, with a mean of 40.98 g kg-1. Correlation coefficients depicted strong positive associations. Two clusters were produced: cluster one had the three anions with SO42¯ being the most important; and cluster two equally had all three anions but with negative t-statistic values. The anions have been continuously displaced as result of their very high mobility as reflected in lower concentrations than those from the control site.

  1. Solvent selection methodology for pharmaceutical processes: Solvent swap

    DEFF Research Database (Denmark)

    Papadakis, Emmanouil; Kumar Tula, Anjan; Gani, Rafiqul

    2016-01-01

    A method for the selection of appropriate solvents for the solvent swap task in pharmaceutical processes has been developed. This solvent swap method is based on the solvent selection method of Gani et al. (2006) and considers additional selection criteria such as boiling point difference, volati...

  2. Biologically informed ecological niche models for an example pelagic, highly mobile species

    Directory of Open Access Journals (Sweden)

    Ingenloff Kate

    2017-03-01

    Full Text Available Background: Although pelagic seabirds are broadly recognised as indicators of the health of marine systems, numerous gaps exist in knowledge of their at-sea distributions at the species level. These gaps have profound negative impacts on the robustness of marine conservation policies. Correlative modelling techniques have provided some information, but few studies have explored model development for non-breeding pelagic seabirds. Here, I present a first phase in developing robust niche models for highly mobile species as a baseline for further development. Methodology: Using observational data from a 12-year time period, 217 unique model parameterisations across three correlative modelling algorithms (boosted regression trees, Maxent and minimum volume ellipsoids were tested in a time-averaged approach for their ability to recreate the at-sea distribution of non-breeding Wandering Albatrosses (Diomedea exulans to provide a baseline for further development. Principle Findings/Results: Overall, minimum volume ellipsoids outperformed both boosted regression trees and Maxent. However, whilst the latter two algorithms generally overfit the data, minimum volume ellipsoids tended to underfit the data. Conclusions: The results of this exercise suggest a necessary evolution in how correlative modelling for highly mobile species such as pelagic seabirds should be approached. These insights are crucial for understanding seabird-environment interactions at macroscales, which can facilitate the ability to address population declines and inform effective marine conservation policy in the wake of rapid global change.

  3. Chromosome Banding in Amphibia. XXXV. Highly Mobile Nucleolus Organizing Regions in Craugastor fitzingeri (Anura, Craugastoridae).

    Science.gov (United States)

    Schmid, Michael; Steinlein, Claus; Feichtinger, Wolfgang; Nanda, Indrajit

    2017-10-24

    A 7-year cytogenetic study on the leaf litter frog Craugastor fitzingeri from Costa Rica and Panama revealed the existence of highly mobile nucleolus organizing regions (NORs) in their genomes. Silver (Ag)-staining of the active NORs demonstrated an exceptional interindividual pattern of NOR distribution at the telomeres of the chromosomes. All individuals examined showed a different and specific NOR location in their karyotypes. Furthermore, intraindividual variation in the NOR sites was found. This observation suggested the existence of mobile NORs in C. fitzingeri. Confirmation of this phenomenon was possible by systematic FISH analysis using an 18S + 28S rDNA probe. The extremely variable number and position of the NORs in C. fitzingeri is best explained by highly mobile NORs that move freely between the telomeres of the chromosomes. These transpositions must occur preferentially in premeiotic, meiotic, or postmeiotic stages, but also at a lower incidence in the somatic tissues of the animals. It is hypothesized that transposable (mobile) elements are closely linked to the NORs or are inserted into the major 18S + 28S rDNA spacers of C. fitzingeri. When such transposable elements spread by transpositions, they can carry with them complete or partial NORs. The present study provides detailed information on various differential chromosome banding techniques, in situ hybridization experiments, chromosomal hypermethylation patterns, determination of the genome size, and analyses of restriction fragment length polymorphisms of the DNA. © 2017 S. Karger AG, Basel.

  4. High mobility AlGaN/GaN devices for β{sup −}-dosimetry

    Energy Technology Data Exchange (ETDEWEB)

    Schmid, Martin; Howgate, John; Ruehm, Werner [Helmholtz Zentrum München, Ingolstädter Landstraße 1, 85764 Neuherberg (Germany); Thalhammer, Stefan, E-mail: stefan.thalhammer@physik.uni-augsburg.de [Universität Augsburg, Universitätsstraße 1, 86159 Augsburg (Germany)

    2016-05-21

    There is a high demand in modern medical applications for dosimetry sensors with a small footprint allowing for unobtrusive or high spatial resolution detectors. To this end we characterize the sensoric response of radiation resistant high mobility AlGaN/GaN semiconductor devices when exposed to β{sup −}-emitters. The samples were operated as a floating gate transistor, without a field effect gate electrode, thus excluding any spurious effects from β{sup −}-particle interactions with a metallic surface covering. We demonstrate that the source–drain current is modulated in dependence on the kinetic energy of the incident β{sup −}-particles. Here, the signal is shown to have a linear dependence on the absorbed energy calculated from Monte Carlo simulations. Additionally, a stable and reproducible sensor performance as a β{sup −}-dose monitor is shown for individual radioisotopes. Our experimental findings and the characteristics of the AlGaN/GaN high mobility layered devices indicate their potential for future applications where small sensor size is necessary, like for instance brachytherapy.

  5. Electron affinities of aromatic hydrocarbons and disproportionation of their radical-anions

    Energy Technology Data Exchange (ETDEWEB)

    Szwarc, M.

    1986-09-01

    Electron affinities of aromatic hydrocarbons measured in the gas-phase and in solutions are compared. The experimental methods used for their determination are briefly reviewed. The reduction yields the respective radical-anions. Radical-anions may undergo disproportionation, a reaction described by the scheme: 2A/sup -/ . , Cat/sup =/ in equilibrium A + A/sup 2-/, 2 Cat/sup +/, K/sub dipr/. The disproportionation constant, K/sub dipr/, is greatly affected by the nature of aromatic hydrocarbon, of the cation, and of the solvent. Variation of each of these factors is illustrated. Variation of the cation and solvent results in changes of the disproportionation constant as large as factors of 10/sup 25/. The causes of these variations are rationalized and discussed in terms of the respective ..delta..H and ..delta..S. Kinetics of disproportionation was investigated by flash-photolysis techniques. The experimental approach is described. The peculiarities of Ba salts deserved some discussion to clarify the nature of those salts. The effect of disproportionation on reactions of radical-anions are described: namely on cis-trans isomerization of stilbenes, on protonation of radical-anions of anthracene an perylene, on dissociation of radical anions of aromatic derivatives ethane, etc.

  6. Anion order in perovskite oxynitrides.

    Science.gov (United States)

    Yang, Minghui; Oró-Solé, Judith; Rodgers, Jennifer A; Jorge, Ana Belén; Fuertes, Amparo; Attfield, J Paul

    2011-01-01

    Transition-metal oxynitrides with perovskite-type structures are an emerging class of materials with optical, photocatalytic, dielectric and magnetoresistive properties that may be sensitive to oxide-nitride order, but the anion-ordering principles were unclear. Here we report an investigation of the representative compounds SrMO(2)N (M = Nb, Ta) using neutron and electron diffraction. This revealed a robust 1O/2(O(0.5)N(0.5)) partial anion order (up to at least 750 °C in the apparently cubic high-temperature phases) that directs the rotations of MO(4)N(2) octahedra in the room-temperature superstructure. The anion distribution is consistent with local cis-ordering of the two nitrides in each octahedron driven by covalency, which results in disordered zigzag M-N chains in planes within the perovskite lattice. Local structures for the full range of oxynitride perovskites are predicted and a future challenge is to tune properties by controlling the order and dimensionality of the anion chains and networks.

  7. Pu Anion Exchange Process Intensification

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-10-06

    This research is focused on improving the efficiency of the anion exchange process for purifying plutonium. While initially focused on plutonium, the technology could also be applied to other ion-exchange processes. Work in FY17 focused on the improvement and optimization of porous foam columns that were initially developed in FY16. These foam columns were surface functionalized with poly(4-vinylpyridine) (PVP) to provide the Pu specific anion-exchange sites. Two different polymerization methods were explored for maximizing the surface functionalization with the PVP. The open-celled polymeric foams have large open pores and large surface areas available for sorption. The fluid passes through the large open pores of this material, allowing convection to be the dominant mechanism by which mass transport takes place. These materials generally have very low densities, open-celled structures with high cell interconnectivity, small cell sizes, uniform cell size distributions, and high structural integrity. These porous foam columns provide advantages over the typical porous resin beads by eliminating the slow diffusion through resin beads, making the anion-exchange sites easily accessible on the foam surfaces. The best performing samples exceeded the Pu capacity of the commercially available resin, and also offered the advantage of sharper elution profiles, resulting in a more concentrated product, with less loss of material to the dilute heads and tails cuts. An alternate approach to improving the efficiency of this process was also explored through the development of a microchannel array system for performing the anion exchange.

  8. THERMODYNAMIC ASSESSMENT OF ANIONIC LIGANDS ...

    African Journals Online (AJOL)

    DJFLEX

    2010-06-30

    Jun 30, 2010 ... ion. This brings about repulsion between the adsorbent and positively charged ion and consequently a reduction in the amount of heavy metal adsorbed at lower pH. (Lee, 1999). The effectiveness of the anionic ligands in the removal of heavy metal ions from aqueous solution seems to be low for the EDTA.

  9. 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.

  10. 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.

  11. Tripodal receptors for cation and anion sensors

    NARCIS (Netherlands)

    Kuswandi, Bambang; Nuriman, [Unknown; Verboom, Willem; Reinhoudt, David

    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

  12. Recognition, Sensing and Separation of Anions

    Indian Academy of Sciences (India)

    Dr Pradyut Ghosh

    2016-11-05

    Nov 5, 2016 ... Anion Recognition. Basic Science: Coordination chemistry of anions. Potential Applications: Development of Selective. Anion Receptor towards. • Chemical Separation. • Clean Environment. • Safe Water. • Chemical Sensing. Inorg. Chem. 2011, 50, 4229. Ion Sensing. Inorg. Chem. 2010, 49, 4447. Chem.

  13. 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.

  14. Halogenated solvent remediation

    Science.gov (United States)

    Sorenson, Jr., Kent S.

    2008-11-11

    Methods for enhancing bioremediation of ground water contaminated with nonaqueous halogenated solvents are disclosed. An illustrative method includes adding an electron donor for microbe-mediated anaerobic reductive dehalogenation of the halogenated solvents, which electron donor enhances mass transfer of the halogenated solvents from residual source areas into the aqueous phase of the ground water. Illustrative electron donors include C.sub.2-C.sub.4 carboxylic acids and hydroxy acids, salts thereof, esters of C.sub.2-C.sub.4 carboxylic acids and hydroxy acids, and mixtures thereof, of which lactic acid, salts of lactic acid--such as sodium lactate, lactate esters, and mixtures thereof are particularly illustrative. The microbes are either indigenous to the ground water, or such microbes can be added to the ground water in addition to the electron donor.

  15. Separation by solvent extraction

    Science.gov (United States)

    Holt, Jr., Charles H.

    1976-04-06

    17. A process for separating fission product values from uranium and plutonium values contained in an aqueous solution, comprising adding an oxidizing agent to said solution to secure uranium and plutonium in their hexavalent state; contacting said aqueous solution with a substantially water-immiscible organic solvent while agitating and maintaining the temperature at from -1.degree. to -2.degree. C. until the major part of the water present is frozen; continuously separating a solid ice phase as it is formed; separating a remaining aqueous liquid phase containing fission product values and a solvent phase containing plutonium and uranium values from each other; melting at least the last obtained part of said ice phase and adding it to said separated liquid phase; and treating the resulting liquid with a new supply of solvent whereby it is practically depleted of uranium and plutonium.

  16. Recognition and sensing of biologically relevant anions in alcohol and mixed alcohol-aqueous solutions using charge neutral cleft-like glycol-derived pyridyl-amidothiourea receptors.

    Science.gov (United States)

    Duke, Rebecca M; McCabe, Thomas; Schmitt, Wolfgang; Gunnlaugsson, Thorfinnur

    2012-04-06

    In this paper, the synthesis and the spectroscopic investigation of new colorimetric receptors for anions 3-6, possessing a glycol chain at the 4-position of the pyridyl ring, and 1 and 2, which lack such a chain, and the X-ray crystal structure of 2 is presented. Structures 3-6 are able to bind to anions in competitive media, such as alcohol or in a mixture of methanol and water, where the anion recognition gives rise to changes in the absorption spectra, which is red-shifted, in 1:1 or 1:2 (sensor/anion) stoichiometry. The anion recognition for 1 and 2 was also investigated in organic solvents and in a 4:1 mixture of DMSO/H(2)O. The binding of 1 to anions such as acetate, phosphate, and fluoride was also evaluated using (1)H NMR in DMSO-d(6).

  17. High mobility group-like proteins of the insect Plodia interpunctella.

    Science.gov (United States)

    Aleporou-Marinou, Vassiliki; Drosos, Yianis; Ninios, Yiannis; Agelopoulou, Barbara; Patargias, Theocharis

    2003-02-01

    Nuclei from Plodia interpunctella larvae contain four major proteins, which are extracted by 5% perchloric acid and 0.35 M NaCl. The proteins have been designated PL1, PL2, PL3, and PL4. The amino acid analyses of these proteins show that they have high proportions of acidic and basic amino acid residues, a property characteristic of the high mobility group (HMG) proteins isolated from vertebrate tissues. Immunological characterication of these proteins clearly shows that PL1, PL2, and PL4 are more closely related to HMG1 dipteran proteins, while PL3 is more closely related to HMG1 dipteran proteins. The possible relatedness of these proteins to HMG proteins is discussed.

  18. Potential role of high mobility group box 1 in viral infectious diseases.

    Science.gov (United States)

    Wang, Haichao; Ward, Mary F; Fan, Xue-Gong; Sama, Andrew E; Li, Wei

    2006-01-01

    A nuclear protein, high mobility group box 1 (HMGB1), is released passively by necrotic cells and actively by macrophages/monocytes in response to exogenous and endogenous inflammatory stimuli. After binding to the receptor for advanced glycation end products (RAGE), or Toll-like receptor 4 (TLR4), HMGB1 activates macrophages/monocytes to express proinflammatory cytokines, chemokines, and adhesion molecules. Pharmacological suppression of its activities or release is protective against lethal endotoxemia and sepsis, establishing HMGB1 as a critical mediator of lethal systemic inflammation. In light of observations that many viruses (e.g., West Nile virus, Salmon anemia virus) can induce passive HMGB1 release, we propose a potential pathogenic role of HMGB1 in viral infectious diseases.

  19. Two-dimensional charge transport in self-organized, high-mobility conjugated polymers

    DEFF Research Database (Denmark)

    Sirringhaus, H.; Brown, P.J.; Friend, R.H.

    1999-01-01

    Self-organization in many solution-processed, semiconducting conjugated polymers results in complex microstructures, in which ordered microcrystalline domains are embedded in an amorphous matrix(I). This has important consequences for electrical properties of these materials: charge transport...... of the ordered microcrystalline domains in the conjugated polymer poly(3-hexylthiophene), P3HT, Self-organization in P3HT results in a lamella structure with two-dimensional conjugated sheets formed by interchain stacking. We find that, depending on processing conditions, the lamellae can adopt two different...... character of the polaronic charge carriers, which exhibit lower relaxation energies than the corresponding radical cations on isolated one-dimensional chains. The possibility of achieving high mobilities via two-dimensional transport in self-organized conjugated lamellae is important for applications...

  20. Accurate on-chip measurement of the Seebeck coefficient of high mobility small molecule organic semiconductors

    Directory of Open Access Journals (Sweden)

    C. N. Warwick

    2015-09-01

    Full Text Available We present measurements of the Seebeck coefficient in two high mobility organic small molecules, 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT and 2,9-didecyl-dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene (C10-DNTT. The measurements are performed in a field effect transistor structure with high field effect mobilities of approximately 3 cm2/V s. This allows us to observe both the charge concentration and temperature dependence of the Seebeck coefficient. We find a strong logarithmic dependence upon charge concentration and a temperature dependence within the measurement uncertainty. Despite performing the measurements on highly polycrystalline evaporated films, we see an agreement in the Seebeck coefficient with modelled values from Shi et al. [Chem. Mater. 26, 2669 (2014] at high charge concentrations. We attribute deviations from the model at lower charge concentrations to charge trapping.

  1. Diketopyrrolopyrrole-diketopyrrolopyrrole-based conjugated copolymer for high-mobility organic field-effect transistors

    KAUST Repository

    Kanimozhi, Catherine K.

    2012-10-10

    In this communication, we report the synthesis of a novel diketopyrrolopyrrole-diketopyrrolopyrrole (DPP-DPP)-based conjugated copolymer and its application in high-mobility organic field-effect transistors. Copolymerization of DPP with DPP yields a copolymer with exceptional properties such as extended absorption characteristics (up to ∼1100 nm) and field-effect electron mobility values of >1 cm 2 V -1 s -1. The synthesis of this novel DPP-DPP copolymer in combination with the demonstration of transistors with extremely high electron mobility makes this work an important step toward a new family of DPP-DPP copolymers for application in the general area of organic optoelectronics. © 2012 American Chemical Society.

  2. Structured back gates for high-mobility two-dimensional electron systems using oxygen ion implantation

    Energy Technology Data Exchange (ETDEWEB)

    Berl, M., E-mail: mberl@phys.ethz.ch; Tiemann, L.; Dietsche, W.; Wegscheider, W. [Solid State Physics Laboratory, ETH Zürich, 8093 Zürich (Switzerland); Karl, H. [Lehrstuhl für Experimentalphysik IV, Universität Augsburg, 86159 Augsburg (Germany)

    2016-03-28

    We present a reliable method to obtain patterned back gates compatible with high mobility molecular beam epitaxy via local oxygen ion implantation that suppresses the conductivity of an 80 nm thick silicon doped GaAs epilayer. Our technique was optimized to circumvent several constraints of other gating and implantation methods. The ion-implanted surface remains atomically flat which allows unperturbed epitaxial overgrowth. We demonstrate the practical application of this gating technique by using magneto-transport spectroscopy on a two-dimensional electron system (2DES) with a mobility exceeding 20 × 10{sup 6} cm{sup 2}/V s. The back gate was spatially separated from the Ohmic contacts of the 2DES, thus minimizing the probability for electrical shorts or leakage and permitting simple contacting schemes.

  3. Cyclotron-resonance-induced photovoltaic effect in high-mobility graphene in the quantum Hall regime

    Science.gov (United States)

    Masubuchi, Satoru; Onuki, Masahiro; Arai, Miho; Watanabe, Kenji; Taniguchi, Takashi; Machida, Tomoki

    2013-03-01

    We have investigated the infrared photoinduced voltage ΔV in high-mobility graphene on hexagonal boron nitride in the quantum Hall regime. We observed ΔV of up to several μV at ν = +/- 2 quantum Hall states under the cyclotron resonance conditions. The dependence of ΔV on the bias current indicates that ΔV signals derive from the photovoltaic effect rather than the bolometric effect. The dependence of ΔV on magnetic field direction and measurement geometry suggest the edge channel transport as an origin of photovoltaic effect. ΔV signals were robust up to T = 180 K, indicating that ΔV signals can be used for developing novel terahertz photodetectors operating at high temperatures.

  4. Dithiopheneindenofluorene (TIF) Semiconducting Polymers with Very High Mobility in Field-Effect Transistors

    KAUST Repository

    Chen, Hu

    2017-07-19

    The charge-carrier mobility of organic semiconducting polymers is known to be enhanced when the energetic disorder of the polymer is minimized. Fused, planar aromatic ring structures contribute to reducing the polymer conformational disorder, as demonstrated by polymers containing the indacenodithiophene (IDT) repeat unit, which have both a low Urbach energy and a high mobility in thin-film-transistor (TFT) devices. Expanding on this design motif, copolymers containing the dithiopheneindenofluorene repeat unit are synthesized, which extends the fused aromatic structure with two additional phenyl rings, further rigidifying the polymer backbone. A range of copolymers are prepared and their electrical properties and thin-film morphology evaluated, with the co-benzothiadiazole polymer having a twofold increase in hole mobility when compared to the IDT analog, reaching values of almost 3 cm2 V−1 s−1 in bottom-gate top-contact organic field-effect transistors.

  5. Cutting edge: extracellular high mobility group box-1 protein is a proangiogenic cytokine.

    Science.gov (United States)

    Mitola, Stefania; Belleri, Mirella; Urbinati, Chiara; Coltrini, Daniela; Sparatore, Bianca; Pedrazzi, Marco; Melloni, Edon; Presta, Marco

    2006-01-01

    The chromosomal high mobility group box-1 (HMGB1) protein acts as a proinflammatory cytokine when released in the extracellular environment by necrotic and inflammatory cells. In the present study, we show that HMGB1 exerts proangiogenic effects by inducing MAPK ERK1/2 activation, cell proliferation, and chemotaxis in endothelial cells of different origin. Accordingly, HMGB1 stimulates membrane ruffling and repair of a mechanically wounded endothelial cell monolayer and causes endothelial cell sprouting in a three-dimensional fibrin gel. In keeping with its in vitro properties, HMGB1 stimulates neovascularization when applied in vivo on the top of the chicken embryo chorioallantoic membrane whose blood vessels express the HMGB1 receptor for advanced glycation end products (RAGE). Accordingly, RAGE blockade by neutralizing Abs inhibits HMGB1-induced neovascularization in vivo and endothelial cell proliferation and membrane ruffling in vitro. Taken together, the data identify HMGB1/RAGE interaction as a potent proangiogenic stimulus.

  6. A guide to calculating habitat-quality metrics to inform conservation of highly mobile species

    Science.gov (United States)

    Bieri, Joanna A.; Sample, Christine; Thogmartin, Wayne E.; Diffendorfer, James E.; Earl, Julia E.; Erickson, Richard A.; Federico, Paula; Flockhart, D. T. Tyler; Nicol, Sam; Semmens, Darius J.; Skraber, T.; Wiederholt, Ruscena; Mattsson, Brady J.

    2018-01-01

    Many metrics exist for quantifying the relative value of habitats and pathways used by highly mobile species. Properly selecting and applying such metrics requires substantial background in mathematics and understanding the relevant management arena. To address this multidimensional challenge, we demonstrate and compare three measurements of habitat quality: graph-, occupancy-, and demographic-based metrics. Each metric provides insights into system dynamics, at the expense of increasing amounts and complexity of data and models. Our descriptions and comparisons of diverse habitat-quality metrics provide means for practitioners to overcome the modeling challenges associated with management or conservation of such highly mobile species. Whereas previous guidance for applying habitat-quality metrics has been scattered in diversified tracks of literature, we have brought this information together into an approachable format including accessible descriptions and a modeling case study for a typical example that conservation professionals can adapt for their own decision contexts and focal populations.Considerations for Resource ManagersManagement objectives, proposed actions, data availability and quality, and model assumptions are all relevant considerations when applying and interpreting habitat-quality metrics.Graph-based metrics answer questions related to habitat centrality and connectivity, are suitable for populations with any movement pattern, quantify basic spatial and temporal patterns of occupancy and movement, and require the least data.Occupancy-based metrics answer questions about likelihood of persistence or colonization, are suitable for populations that undergo localized extinctions, quantify spatial and temporal patterns of occupancy and movement, and require a moderate amount of data.Demographic-based metrics answer questions about relative or absolute population size, are suitable for populations with any movement pattern, quantify demographic

  7. High Mobility and HIV Prevalence Among Female Market Traders in East Africa in 2014.

    Science.gov (United States)

    Camlin, Carol S; El Ayadi, Alison M; Kwena, Zachary A; McFarland, Willi; Johnson, Mallory O; Neilands, Torsten B; Bukusi, Elizabeth A; Cohen, Craig R

    2017-04-15

    The contribution of women's mobility to the HIV/AIDS epidemic in Africa is poorly understood, despite women's high mobility and evidence that it is associated with higher-risk sexual behavior. We sought to measure levels of mobility, HIV prevalence, and related risk behaviors among female traders in Kisumu, Kenya. We used global positioning system mapping to develop a probability-based sample and recruited 305 female market traders for participation in a survey and voluntary HIV counseling and testing in 2014. We estimated HIV prevalence and fitted logistic regression models to measure associations between mobility, risk behaviors, and HIV infection. HIV prevalence was 25.6% (95% confidence interval: 21.0 to 30.8); 11.5% had migrated (changed residence, over county, or national boundary) in the past year and 39.3% in the past 5 years. More than one-third (38.3%) spent nights away from main residence in the past month, with 11.4% spending more than a week away. Multiple partners were reported by 13.1% of women in the last year; 16% of married women reported a concurrent partnership. Mobility was not significantly associated with HIV prevalence, although recent short-term mobility was significantly correlated with higher numbers of sexual partners in the past year. Female market traders were highly mobile, and HIV prevalence among traders was higher than in the general population of women of reproductive age in Kisumu (15.3% in 2013), and Nyanza Province, Kenya (16.1% in 2012). High HIV prevalence and risk behavior among women in this study warrant accelerated attention to HIV prevention and care needs of mobile women, including market traders.

  8. 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.

  9. 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.

  10. 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...... and the expulsion of anions; a broad anodic peak centered at ca. - 0.5 V representing the expulsion of cations; and a second broad peak at +0.2 to +0.5 V corresponding to anions being inserted. Although the motion of cations is the most important, as expected, there is a significant anion contribution, thereby...... 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...

  11. Solvent engineering and other reaction design methods for favouring enzyme-catalysed synthesis

    DEFF Research Database (Denmark)

    Zeuner, Birgitte

    important for FAE activity and stability in IL-buffer (15% v/v) systems. The quantum chemistry-based COSMO-RS method was applied for explaining the IL anion effect in terms of hydrogen bonding capacity. Furthermore, the usefulness of COSMO-RS and other thermodynamically based tools in solvent selection....... However, both FAEs catalysed the feruloylation and/or sinapoylation of solvent cation C2OHMIm+, thus underlining the broad acceptor specificity of FAEs and their potential for future solvent reactions. An engineered sialidase from Trypanosoma rangeli, Tr6, catalyses trans-sialylation but the yield...

  12. ONSITE SOLVENT RECOVERY

    Science.gov (United States)

    This study evaluated the product quality, waste reduction/pollution prevention, and economic aspects of three technologies for onsite solvent recovery. The technologies were (1) atmospheric batch distillation, (2) vacuum heat-pump distillation, and (3) low-emission vapor degreas...

  13. Organic solvent topical report

    Energy Technology Data Exchange (ETDEWEB)

    Cowley, W.L.

    1998-04-30

    This report is the technical basis for the accident and consequence analyses used in the Hanford Tank Farms Basis for Interim Operation. The report also contains the scientific and engineering information and reference material needed to understand the organic solvent safety issue. This report includes comments received from the Chemical Reactions Subcommittee of the Tank Advisory Panel.

  14. Organic solvent topical report

    Energy Technology Data Exchange (ETDEWEB)

    COWLEY, W.L.

    1999-05-13

    This report provides the basis for closing the organic solvent safety issue. Sufficient information is presented to conclude that risk posed by an organic solvent fire is within risk evaluation guidelines. This report updates information contained in Analysis of Consequences of Postulated Solvent Fires in Hanford Site Waste Tanks. WHC-SD-WM-CN-032. Rev. 0A (Cowley et al. 1996). However, this document will not replace Cowley et al (1996) as the primary reference for the Basis for Interim Operation (BIO) until the recently submitted BIO amendment (Hanson 1999) is approved by the US Department of Energy. This conclusion depends on the use of controls for preventing vehicle fuel fires and for limiting the use of flame cutting in areas where hot metal can fall on the waste surface.The required controls are given in the Tank Waste Remediation System Technical Safety Requirements (Noorani 1997b). This is a significant change from the conclusions presented in Revision 0 of this report. Revision 0 of this calcnote concluded that some organic solvent fire scenarios exceeded risk evaluation guidelines, even with controls imposed.

  15. From anion receptors to transporters.

    Science.gov (United States)

    Gale, Philip A

    2011-03-15

    Cystic fibrosis is the most well-known of a variety of diseases termed channelopathies, in which the regulation of ion transport across cell membranes is so disrupted that the threshold of a pathology is passed. The human toll exacted by these diseases has led a number of research groups, including our own, to create compounds that mediate ion transport across lipid bilayers. In this Account, we discuss three classes of synthetic compounds that were refined to bind and transport anions across lipid bilayer membranes. All of the compounds were originally designed as anion receptors, that is, species that would simply create stable complexes with anions, but were then further developed as transporters. By studying structurally simple systems and varying their properties to change the degree of preorganization, the affinity for anions, or the lipophilicity, we have begun to rationalize why particular anion transport mechanisms (cotransport or antiport processes) occur in particular cases. For example, we have studied the chloride transport properties of receptors based on the closely related structures of isophthalamide and pyridine-2,6-dicarboxamide: the central ring in each case was augmented with pendant methylimidazole groups designed to cotransport H(+) and Cl(-). We observed that the more preorganized pyridine-based receptor was the more efficient transporter, a finding replicated with a series of isophthalamides in which one contained hydroxyl groups designed to preorganize the receptor. This latter class of compound, together with the natural product prodigiosin, can transport bicarbonate (as part of a chloride/bicarbonate antiport process) across lipid bilayer membranes. We have also studied the membrane transport properties of calix[4]pyrroles. Although the parent meso-octamethylcalix[4]pyrrole functions solely as a Cs(+)/Cl(-) cotransporter, other compounds with increased anion affinities can function through an antiport process. One example is octafluoro

  16. Anion Sensing Properties of New Colorimetric Chemosensors Based on Thiourea and Urea Moieties

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Dong Wan; Kim, Jung Hwan; Hwang, Jae Young; Park, Jong Keun; Kim, Jae Sang [Gyeongsang National University, Jinju (Korea, Republic of)

    2012-04-15

    A new colorimetric sensors containing thiourea (1-(4-nitrophenyl)-3-quinolin-6-ylthiourea: 1) and urea(1-(4- nitrophenyl)-3-quinolin-6-ylurea: 2) moieties for fluoride were designed and synthesized. These simple receptors were characterized their stoichiometry, and investigates the mechanism of their selectivity as anion receptors. The addition of tetrabutylammonium fluoride salts to the solution of receptors caused a dramatically and clearly observable color changes from colorless to yellow. To examine their application as anion receptors by UV-vis and {sup 1}H NMR spectroscopy results revealed their higher selectivity for fluoride ion than other anions. The receptors and fluoride ion formed a 1:1 stoichiometry complex through strong hydrogen bonding interactions in the first step, followed by a process of deprotonation in presence of an excess of F{sup -} in DMSO solvent

  17. 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.

  18. Anion bridges drive salting out of a simple amphiphile from aqueous solution

    OpenAIRE

    Bowron, D. T.; Finney, J. L.

    2002-01-01

    Neutron diffraction with isotope substitution has been used to determine the structural changes that occur on the addition of a simple salting-out agent to a dilute aqueous alcohol solution. The striking results obtained demonstrate a relatively simple process occurs in which interamphiphile anionic salt bridges are formed between the polar groups of the alcohol molecules. These ion bridges drive an increase in the exposure of the alcohol molecule nonpolar surface to the solvent water and hen...

  19. A Convenient Synthesis of Triflate Anion Ionic Liquids and Their Properties

    Directory of Open Access Journals (Sweden)

    Peter Sartori

    2012-05-01

    Full Text Available A solvent- and halogen-free synthesis of high purity triflate ionic liquids via direct alkylation of organic bases (amines, phosphines or heterocyclic compounds with methyl and ethyl trifluoromethanesulfonate (methyl and ethyl triflate has been developed. Cheap and non-toxic dimethyl and diethyl carbonate serve as source for the methyl and ethyl groups in the preparation of methyl and ethyl triflate by this invented process. The properties of ionic liquids containing the triflate anion are determined and discussed.

  20. Relationship study of partition coefficients between ionic liquid and headspace for organic solvents by HS-GC.

    Science.gov (United States)

    Ni, Meiping; Sun, Ting; Zhang, Lin; Liu, Yan; Xu, Meng; Jiang, Ye

    2014-01-15

    A general study was carried out to investigate the relationship between analytes (organic solvents) and matrix medium (ionic liquids, ILs) by headspace gas chromatography (HS-GC) in order to provide a guidance to choose a suitable matrix medium during the process of experiment. Thirteen ILs contained different cations or anions and two kinds of organic solvents (alkylogens and aprotic solvents which involved ability of pro-proton) performed different interactions with ILs were chosen in this study. The concentrations of analytes in headspace were determined by HS-GC and then logK (the logarithm of concentration radio between matrix medium and headspace) was calculated respectively. Factors which affect logK, such as logPO/W (the logarithm of the octanol/water partition coefficient for a solvent) for different cations (including parent nucleus and alkyl chains) and anions of ILs, were investigated. The results indicated that the longer alkyl chains, the lower polarity of parent nucleus and the higher polarity of anions performed the higher headspace efficiency for alkylogens. Meanwhile, the shorter alkyl chains and the lower polarity of parent nucleus make the higher headspace efficiency for aprotic solvents which involved ability of pro-proton. For both kinds of organic solvents, anions of ILs performed little influences to headspace efficiency. The relationship between ILs and organic solvents was primarily investigated and a helpful guidance was provided for the application of ILs as matrix medium to analyze solvents by HS-GC. The model was successfully used to determine the organic residual solvents in ketoconanzale to choose a suitable ionic liquid during the process of HS-GC. Copyright © 2013 Elsevier B.V. All rights reserved.

  1. Effects of Anion Mobility on Electrochemical Behaviors of Lithium–Sulfur Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Han, Kee Sung [Environmental; Joint Center for Energy Storage Research (JCESR), Lemont, Illinois 60439, United States; Chen, Junzheng [Energy; Joint Center for Energy Storage Research (JCESR), Lemont, Illinois 60439, United States; Cao, Ruiguo [Energy; Joint Center for Energy Storage Research (JCESR), Lemont, Illinois 60439, United States; Rajput, Nav Nidhi [Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States; Joint Center for Energy Storage Research (JCESR), Lemont, Illinois 60439, United States; Murugesan, Vijayakumar [Energy; Joint Center for Energy Storage Research (JCESR), Lemont, Illinois 60439, United States; Shi, Lili [Energy; Joint Center for Energy Storage Research (JCESR), Lemont, Illinois 60439, United States; Pan, Huilin [Energy; Joint Center for Energy Storage Research (JCESR), Lemont, Illinois 60439, United States; Zhang, Ji-Guang [Energy; Joint Center for Energy Storage Research (JCESR), Lemont, Illinois 60439, United States; Liu, Jun [Energy; Joint Center for Energy Storage Research (JCESR), Lemont, Illinois 60439, United States; Persson, Kristin A. [Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States; Department; amp, Engineering, University of California, Berkeley, California 94720-1760, United States; Joint Center for Energy Storage Research (JCESR), Lemont, Illinois 60439, United States; Mueller, Karl T. [Physical; Joint Center for Energy Storage Research (JCESR), Lemont, Illinois 60439, United States

    2017-10-27

    The electrolyte is a crucial component of lithium-sulfur (Li-S) batteries, as it controls polysulfide dissolution, charge shuttling processes, and solid-electrolyte interphase (SEI) layer formation. Experimentally, the overall performance of Li-S batteries varies with choice of solvent system and Li-salt used in the electrolyte, and a lack of predictive understanding about the effects of individual electrolyte components inhibits the rational design of electrolytes for Li-S batteries. Here we analyze the role of the counter anions of common Li salts (such as TfO-, FSI-, TFSI-, and TDI-) when dissolved in DOL/DME (1:1 vol.) for use in Li-S batteries. The evolution of ion-ion and ion-solvent interactions due to vari-ous anions was analyzed using 17O NMR and pulsed-field gradient (PFG) NMR and then correlated with electrochemi-cal performance in Li-S cells. These data reveal that the for-mation of the passivation layer on the anode and the loss of active materials from the cathode (evidenced by polysulfide dissolution) are related to anion mobility and affinity with lithium polysulfide, respectively. For future electrolyte de-sign, anions with lower mobility and weaker interactions with lithium polysulfides may be superior candidates for increasing the long-term stability of Li-S batteries.

  2. High mobility group box-1 and its clinical value in breast cancer

    Directory of Open Access Journals (Sweden)

    Sun S

    2015-02-01

    Full Text Available Shanping Sun,1,2 Wei Zhang,2 Zhaoqing Cui,2 Qi Chen,2 Panpan Xie,2 Changxin Zhou,2 Baoguo Liu,2 Xiangeng Peng,2 Yang Zhang21Department of Breast Surgery, Qilu Hospital of Shandong University, Shandong, People’s Republic of China; 2Department of Breast and Thyroid Surgery, Liaocheng People’s Hospital, Liaocheng, Shandong Province, People’s Republic of ChinaBackground: High mobility group box-1 (HMGB1 is a factor regulating malignant tumorigenesis, proliferation, and metastasis, and is associated with poor clinical pathology in various human cancers. We investigated the differential concentrations of HMGB1 in tissues and sera, and their clinical value for diagnosis in patients with breast cancer, benign breast disease, and healthy individuals.Methods: HMGB1 levels in tumor tissues, adjacent normal tissues, and benign breast disease tissues was detected via immunohistochemistry. Serum HMGB1 was measured using an enzyme-linked immunosorbent assay in 56 patients with breast cancer, 25 patients with benign breast disease, and 30 healthy control subjects. The clinicopathological features of the patients were compared. Tissues were evaluated histopathologically by pathologists.Results: HMGB1 levels in the tissues and sera of patients with breast cancer were significantly higher than those in patients with benign breast disease or normal individuals. The 56 cancer patients were classified as having high tissue HMGB1 levels (n=41 or low tissue HMGB1 levels (n=15, but the corresponsive serum HMGB1 in these two groups was not significantly different. HMGB1 levels in breast cancer tissues significantly correlated with differentiation grade, lymphatic metastasis, and tumor-node-metastasis stage, but not patient age, tumor size, or HER-2/neu expression; no association between serum HMGB1 levels and these clinicopathological parameters was found. The sensitivity and specificity of tissue HMGB1 levels for the diagnosis of breast cancer were 73.21% and 84

  3. Transformational Electronics: Towards Flexible Low-Cost High Mobility Channel Materials

    KAUST Repository

    Nassar, Joanna M.

    2014-05-01

    For the last four decades, Si CMOS technology has been advancing with Moore’s law prediction, working itself down to the sub-20 nm regime. However, fundamental problems and limitations arise with the down-scaling of transistors and thus new innovations needed to be discovered in order to further improve device performance without compromising power consumption and size. Thus, a lot of studies have focused on the development of new CMOS compatible architectures as well as the discovery of new high mobility channel materials that will allow further miniaturization of CMOS transistors and improvement of device performance. Pushing the limits even further, flexible and foldable electronics seem to be the new attractive topic. By being able to make our devices flexible through a CMOS compatible process, one will be able to integrate hundreds of billions of more transistors in a small volumetric space, allowing to increase the performance and speed of our electronics all together with making things thinner, lighter, smaller and even interactive with the human skin. Thus, in this thesis, we introduce for the first time a cost-effective CMOS compatible approach to make high-k/metal gate devices on flexible Germanium (Ge) and Silicon-Germanium (SiGe) platforms. In the first part, we will look at the various approaches in the literature that has been developed to get flexible platforms, as well as we will give a brief overview about epitaxial growth of Si1-xGex films. We will also examine the electrical properties of the Si1-xGex alloys up to Ge (x=1) and discuss how strain affects the band structure diagram, and thus the mobility of the material. We will also review the material growth properties as well as the state-of-the-art results on high mobility metal-oxide semiconductor capacitors (MOSCAPs) using strained SiGe films. Then, we will introduce the flexible process that we have developed, based on a cost-effective “trench-protect-release-reuse” approach, utilizing

  4. Interstellar Anions: The Role of Quantum Chemistry.

    Science.gov (United States)

    Fortenberry, Ryan C

    2015-10-01

    Six anions have been conclusively detected in the interstellar medium (ISM). They all arrived within a five-year window ending five years ago. Why have no new anions been detected? It is likely a lack of laboratory data for novel anions. This work reviews the role that valence and dipole-bound excited states may play in the formation, detection, and lifetime of anions that may yet be observed in the ISM and how quantum chemistry enhances this understanding. The list of interstellar anions has certainly not been exhausted by any means, but electronic, spectroscopic, and structural data must be provided to aid in any future detections. Quantum chemistry has the flexibility and completeness to provide a full picture of these systems and has shown exceptional accuracies of late. The work reviewed herein gives an overview of what quantum chemical computations have produced and will continue to provide related to anions and how this will enhance both laboratory experiment and astronomical observation.

  5. Microscopic observation of highly mobile charge carriers in organic transistors of semicrystalline conducting polymers

    Science.gov (United States)

    Kawamura, Shinya; Wakamatsu, Ayato; Kuroda, Shin-ichi; Takenobu, Taishi; Tanaka, Hisaaki

    2018-02-01

    Charge carrier dynamics in organic field-effect transistors (OFETs) of semicrystalline conducting polymers poly(2,5-bis(3-hexadecylthiophene-2-yl)thieno[3,2-b]thiophene) (PBTTT) and poly(3-hexylthiophene) (P3HT) have been investigated down to 4 K by field-induced electron spin resonance (FI-ESR) spectroscopy. The highly mobile nature of charge carriers within the ordered regions of the polymers has been clarified from the observation of the motional narrowing effect of the ESR spectra even below 30 K, where device operation cannot be observed presumably owing to the effect of domain boundaries. The activation energy of carrier motion observed by ESR has been determined as 17 meV for PBTTT and 13 meV for P3HT, which are an order of magnitude smaller than that of FET mobility (>110 meV) obtained for the same devices. These results demonstrate that the intrinsic carrier mobility within the ordered region is much higher than that expected from the macroscopic transport measurements in the semicrystalline polymers.

  6. Endotoxin tolerance alleviates experimental acute liver failure via inhibition of high mobility group box 1.

    Science.gov (United States)

    Yang, Nai-Bin; Ni, Shun-Lan; Li, Shan-Shan; Zhang, Sai-Nan; Hu, Dan-Ping; Lu, Ming-Qin

    2015-01-01

    High mobility group box 1 (HMGB1) has been widely reported to mediate damage caused by inflammatory responses. The aim of our study is to investigate the role of HMGB1 in endotoxin tolerance (ET) alleviating inflammation of acute liver failure (ALF) rats and its possible signaling mechanism. To mimic ET, male Sprague-Dawley rats were pretreated with low dose of lipopolysaccharide (LPS) (0.1 mg/kg once a day intraperitoneally for consecutive five days) before subsequent ALF induction. ALF was induced by intraperitoneal administration of D-GalN/LPS. ET induced by LPS pretreatment significantly improved the survival rate of ALF rats. Moreover, after ALF induction, ET+ALF rats exhibited lower serum enzyme (ALT, AST and TBiL) levels, lower production of inflammatory cytokines (IL-6, TNF-a and HMGB1) and more minor liver histopathological damage than ALF rats. ET+ALF rats showed enhanced expression levels of HMGB1, decreased levels of STAT1 and p-STAT1, augmented expression of SOCS1 in liver tissues than ALF rats. These results indicated that ET induced by low-dose LPS pretreatment may alleviate inflammation and liver injury in experimental acute liver failure rats mainly through inhibition of hepatic HMGB1 translocation and release.

  7. Increased serum levels of high mobility group box 1 protein in patients with autistic disorder.

    Science.gov (United States)

    Emanuele, Enzo; Boso, Marianna; Brondino, Natascia; Pietra, Stefania; Barale, Francesco; Ucelli di Nemi, Stefania; Politi, Pierluigi

    2010-05-30

    High mobility group box 1 (HMGB1) is a highly conserved, ubiquitous protein that functions as an activator for inducing the immune response and can be released from neurons after glutamate excitotoxicity. The objective of the present study was to measure serum levels of HMGB1 in patients with autistic disorder and to study their relationship with clinical characteristics. We enrolled 22 adult patients with autistic disorder (mean age: 28.1+/-7.7 years) and 28 age- and gender-matched healthy controls (mean age: 28.7+/-8.1 years). Serum levels of HMGB1 were measured by enzyme-linked immunosorbent assay (ELISA). Compared with healthy subjects, serum levels of HMGB1 were significantly higher in patients with autistic disorder (10.8+/-2.6 ng/mL versus 5.6+/-2.5 ng/mL, respectively, Pautistic disorder. Increased HMGB1 may be a biological correlate of the impaired reciprocal social interactions in this neurodevelopmental disorder. Copyright 2010 Elsevier Inc. All rights reserved.

  8. Contributions of high mobility group box protein in experimental and clinical acute lung injury.

    Science.gov (United States)

    Ueno, Hiroshi; Matsuda, Tomoyuki; Hashimoto, Satoru; Amaya, Fumimasa; Kitamura, Yoshihiro; Tanaka, Masaki; Kobayashi, Atsuko; Maruyama, Ikuro; Yamada, Shingo; Hasegawa, Naoki; Soejima, Junko; Koh, Hidefumi; Ishizaka, Akitoshi

    2004-12-15

    This study was performed to examine the putative role of high mobility group box (HMGB) protein in the pathogenesis of acute lung injury (ALI). Observations were made (1) in 21 patients who were septic with ALI and 15 patients with normal lung function and (2) in a mouse model 24 hours after intratracheal instillation of lipopolysaccharide (LPS). The concentrations of HMGB1 were increased in plasma and lung epithelial lining fluid of patients with ALI and mice instilled with LPS. LPS-induced ALI was mitigated by anti-HMGB1 antibody. Although this protein was not detected in the plasma of control humans or mice, the concentrations of HMGB1 in lung epithelial lining fluid or in bronchoalveolar lavage fluid were unexpectedly high. The nuclear expression of HMGB1 was apparent in epithelial cells surrounding terminal bronchioles in normal mice, whereas its nuclear and cytoplasmic expression was observed in alveolar macrophages in LPS-instilled mice. Lung instillation of HMGB2 did not cause as much inflammation as HMGB1. Extracellular HMGB1 may play a key role in the pathogenesis of clinical and experimental ALI. However, its expression in normal airways is noteworthy and suggests that it also plays a physiologic role in the lung.

  9. Paradoxical role of high mobility group box 1 in glioma: a suppressor or a promoter?

    Directory of Open Access Journals (Sweden)

    Richard A. Seidu

    2017-03-01

    Full Text Available Gliomas represent 60% of primary intracranial brain tumors and 80% of all malignant types, with highest morbidity and mortality worldwide. Although glioma has been extensively studied, the molecular mechanisms underlying its pathology remain poorly understood. Clarification of the molecular mechanisms involved in their development and/or treatment resistance is highly required. High mobility group box 1 protein (HMGB1 is a nuclear protein that can also act as an extracellular trigger of inflammation, proliferation and migration, through receptor for advanced glycation end products and toll like receptors in a number of cancers including gliomas. It is known that excessive release of HMGB1 in cancer leads to unlimited replicative potential, ability to develop blood vessels (angiogenesis, evasion of programmed cell death (apoptosis, self-sufficiency in growth signals, insensitivity to inhibitors of growth, inflammation, tissue invasion and metastasis. In this review we explore the mechanisms by which HMGB1 regulates apoptosis and autophagy in glioma. We also looked at how HMGB1 mediates glioma regression and promotes angiogenesis as well as possible signaling pathways with an attempt to provide potential therapeutic targets for the treatment of glioma.

  10. Monte Carlo simulation of ballistic transport in high-mobility channels

    Energy Technology Data Exchange (ETDEWEB)

    Sabatini, G; Marinchio, H; Palermo, C; Varani, L; Daoud, T; Teissier, R [Institut d' Electronique du Sud (CNRS UMR 5214) - Universite Montpellier II (France); Rodilla, H; Gonzalez, T; Mateos, J, E-mail: sabatini@ies.univ-montp2.f [Departamento de Fisica Aplicada - Universidad de Salamanca (Spain)

    2009-11-15

    By means of Monte Carlo simulations coupled with a two-dimensional Poisson solver, we evaluate directly the possibility to use high mobility materials in ultra fast devices exploiting ballistic transport. To this purpose, we have calculated specific physical quantities such as the transit time, the transit velocity, the free flight time and the mean free path as functions of applied voltage in InAs channels with different lengths, from 2000 nm down to 50 nm. In this way the transition from diffusive to ballistic transport is carefully described. We remark a high value of the mean transit velocity with a maximum of 14x10{sup 5} m/s for a 50 nm-long channel and a transit time shorter than 0.1 ps, corresponding to a cutoff frequency in the terahertz domain. The percentage of ballistic electrons and the number of scatterings as functions of distance are also reported, showing the strong influence of quasi-ballistic transport in the shorter channels.

  11. Identification and Characterization of the Lamprey High-Mobility Group Box 1 Gene

    Science.gov (United States)

    Pang, Yue; Xiao, Rong; Liu, Xin; Li, Qingwei

    2012-01-01

    High-mobility group box 1 (HMGB1), a highly conserved DNA-binding protein, plays an important role in maintaining nucleosome structures, transcription, and inflammation. We identified a homolog of HMGB1 in the Japanese lamprey (Lampetra japonica). The Lampetra japonica HMGB1 gene (Lj-HMGB1) has over 70% sequence identity with its homologs in jawed vertebrates. Despite the reasonably high sequence identity with other HMGB1 proteins, Lj-HMGB1 did not group together with these proteins in a phylogenetic analysis. We examined Lj-HMGB1 expression in lymphocyte-like cells, and the kidneys, heart, gills, and intestines of lampreys before and after the animals were challenged with lipopolysaccharide (LPS) and concanavalin A (ConA). Lj-HMGB1 was initially expressed at a higher level in the heart, but after treatment with LPS and ConA only the gills demonstrated a significant up-regulation of expression. The recombinant Lj-HMGB1 (rLj-HMGB1) protein bound double-stranded DNA and induced the proliferation of human adenocarcinoma cells to a similar extent as human HMGB1. We further revealed that Lj-HMGB1 was able to induce the production of tumor necrosis factor-α (TNF-α), a pro-inflammatory mediator, in activated human acute monocytic leukemia cells. These results suggest that lampreys use HMGB1 to activate their innate immunity for the purpose of pathogen defense. PMID:22563397

  12. Identification and characterization of the lamprey high-mobility group box 1 gene.

    Directory of Open Access Journals (Sweden)

    Yue Pang

    Full Text Available High-mobility group box 1 (HMGB1, a highly conserved DNA-binding protein, plays an important role in maintaining nucleosome structures, transcription, and inflammation. We identified a homolog of HMGB1 in the Japanese lamprey (Lampetra japonica. The Lampetra japonica HMGB1 gene (Lj-HMGB1 has over 70% sequence identity with its homologs in jawed vertebrates. Despite the reasonably high sequence identity with other HMGB1 proteins, Lj-HMGB1 did not group together with these proteins in a phylogenetic analysis. We examined Lj-HMGB1 expression in lymphocyte-like cells, and the kidneys, heart, gills, and intestines of lampreys before and after the animals were challenged with lipopolysaccharide (LPS and concanavalin A (ConA. Lj-HMGB1 was initially expressed at a higher level in the heart, but after treatment with LPS and ConA only the gills demonstrated a significant up-regulation of expression. The recombinant Lj-HMGB1 (rLj-HMGB1 protein bound double-stranded DNA and induced the proliferation of human adenocarcinoma cells to a similar extent as human HMGB1. We further revealed that Lj-HMGB1 was able to induce the production of tumor necrosis factor-α (TNF-α, a pro-inflammatory mediator, in activated human acute monocytic leukemia cells. These results suggest that lampreys use HMGB1 to activate their innate immunity for the purpose of pathogen defense.

  13. Anabolic Properties of High Mobility Group Box Protein-1 in Human Periodontal Ligament Cells In Vitro

    Directory of Open Access Journals (Sweden)

    Michael Wolf

    2014-01-01

    Full Text Available High mobility group box protein-1 (HMGB1 is mainly recognized as a chemoattractant for macrophages in the initial phase of host response to pathogenic stimuli. However, recent findings provide evidence for anabolic properties in terms of enhanced proliferation, migration, and support of wound healing capacity of mesenchymal cells suggesting a dual role of the cytokine in the regulation of immune response and subsequent regenerative processes. Here, we examined potential anabolic effects of HMGB1 on human periodontal ligament (PDL cells in the regulation of periodontal remodelling, for example, during orthodontic tooth movement. Preconfluent human PDL cells (hPDL were exposed to HMGB1 protein and the influence on proliferation, migration, osteogenic differentiation, and biomineralization was determined by MTS assay, real time PCR, immunofluorescence cytochemistry, ELISA, and von Kossa staining. HMGB1 protein increased hPDL cell proliferation, migration, osteoblastic marker gene expression, and protein production as well as mineralized nodule formation significantly. The present findings support the dual character of HMGB1 with anabolic therapeutic potential that might support the reestablishment of the structural and functional integrity of the periodontium following periodontal trauma such as orthodontic tooth movement.

  14. High Mobility Group B Proteins, Their Partners, and Other Redox Sensors in Ovarian and Prostate Cancer

    Directory of Open Access Journals (Sweden)

    Aida Barreiro-Alonso

    2016-01-01

    Full Text Available Cancer cells try to avoid the overproduction of reactive oxygen species by metabolic rearrangements. These cells also develop specific strategies to increase ROS resistance and to express the enzymatic activities necessary for ROS detoxification. Oxidative stress produces DNA damage and also induces responses, which could help the cell to restore the initial equilibrium. But if this is not possible, oxidative stress finally activates signals that will lead to cell death. High mobility group B (HMGB proteins have been previously related to the onset and progressions of cancers of different origins. The protein HMGB1 behaves as a redox sensor and its structural changes, which are conditioned by the oxidative environment, are associated with different functions of the protein. This review describes recent advances in the role of human HMGB proteins and other proteins interacting with them, in cancerous processes related to oxidative stress, with special reference to ovarian and prostate cancer. Their participation in the molecular mechanisms of resistance to cisplatin, a drug commonly used in chemotherapy, is also revised.

  15. Highly mobile ferroelastic domain walls in compositionally graded ferroelectric thin films.

    Science.gov (United States)

    Agar, J C; Damodaran, A R; Okatan, M B; Kacher, J; Gammer, C; Vasudevan, R K; Pandya, S; Dedon, L R; Mangalam, R V K; Velarde, G A; Jesse, S; Balke, N; Minor, A M; Kalinin, S V; Martin, L W

    2016-05-01

    Domains and domain walls are critical in determining the response of ferroelectrics, and the ability to controllably create, annihilate, or move domains is essential to enable a range of next-generation devices. Whereas electric-field control has been demonstrated for ferroelectric 180° domain walls, similar control of ferroelastic domains has not been achieved. Here, using controlled composition and strain gradients, we demonstrate deterministic control of ferroelastic domains that are rendered highly mobile in a controlled and reversible manner. Through a combination of thin-film growth, transmission-electron-microscopy-based nanobeam diffraction and nanoscale band-excitation switching spectroscopy, we show that strain gradients in compositionally graded PbZr1-xTixO3 heterostructures stabilize needle-like ferroelastic domains that terminate inside the film. These needle-like domains are highly labile in the out-of-plane direction under applied electric fields, producing a locally enhanced piezoresponse. This work demonstrates the efficacy of novel modes of epitaxy in providing new modalities of domain engineering and potential for as-yet-unrealized nanoscale functional devices.

  16. Fabrication and characterization of high-mobility solution-based chalcogenide thin-film transistors

    KAUST Repository

    Mejia, Israel I.

    2013-01-01

    We report device and material considerations for the fabrication of high-mobility thin-film transistors (TFTs) compatible with large-area and inexpensive processes. In particular, this paper reports photolithographically defined n-type TFTs (n-TFTs) based on cadmium sulfide (CdS) films deposited using solution-based techniques. The integration process consists of four mask levels with a maximum processing temperature of 100 °C. The TFT performance was analyzed in terms of the CdS semiconductor thickness and as a function of postdeposition annealing in a reducing ambient. The IonI off ratios are ∼107 with field-effect mobilities of ∼5.3 and ∼4.7cm2V̇s for Al and Au source-drain contacts, respectively, using 70 nm of CdS. Transmission electron microscopy and electron energy loss spectroscopy were used to analyze the CdS-metal interfaces. © 1963-2012 IEEE.

  17. Comprehensive review on the development of high mobility in oxide thin film transistors

    Science.gov (United States)

    Choi, Jun Young; Lee, Sang Yeol

    2017-11-01

    Oxide materials are one of the most advanced key technology in the thin film transistors (TFTs) for the high-end of device applications. Amorphous oxide semiconductors (AOSs) have leading technique for flat panel display (FPD), active matrix organic light emitting display (AMOLED) and active matrix liquid crystal display (AMLCD) due to their excellent electrical characteristics, such as field effect mobility ( μ FE ), subthreshold swing (S.S) and threshold voltage ( V th ). Covalent semiconductor like amorphous silicon (a-Si) is attributed to the anti-bonding and bonding states of Si hybridized orbitals. However, AOSs have not grain boundary and excellent performances originated from the unique characteristics of AOS which is the direct orbital overlap between s orbitals of neighboring metal cations. High mobility oxide TFTs have gained attractive attention during the last few years and today in display industries. It is progressively developed to increase the mobility either by exploring various oxide semiconductors or by adopting new TFT structures. Mobility of oxide thin film transistor has been rapidly increased from single digit to higher than 100 cm2/V·s in a decade. In this review, we discuss on the comprehensive review on the mobility of oxide TFTs in a decade and propose bandgap engineering and novel structure to enhance the electrical characteristics of oxide TFTs.

  18. Epochal neuroinflammatory role of high mobility group box 1 in central nervous system diseases

    Directory of Open Access Journals (Sweden)

    Seidu A. Richard

    2017-05-01

    Full Text Available The central nervous system (CNS is enriched with a developed reaction reserve dubbed “neuroinflammation”, which facilitates it to cope with pathogens, toxins, traumata and degeneration. Inflammation is a significant biological activity in reaction to injury, infection, and trauma agonized by cells or tissues. A positive inflammatory reaction mechanism removes attacking pathogens, initiating wound healing and angiogenesis. The High Mobility Group Box 1 (HMGB1 protein is abundant and ubiquitous nuclear proteins that bind to DNA, nucleosome and other multi-protein complexes in a dynamic and reversible fashion to regulate DNA processing in the context of chromatin. Complex genetic and physiological variations as well as environmental factors that drive emergence of chromosomal instability, development of unscheduled cell death, skewed differentiation, and altered metabolism are central to the pathogenesis of human diseases and disorders. HMGB1 protein, senses and coordinates the cellular stress response and plays a critical role not only inside of the cell as a DNA chaperone, chromosome guardian, autophagy sustainer, and protector from apoptotic cell death, but also outside the cell as the prototypic damage associated molecular pattern molecule (DAMP. This DAMP, in conjunction with other factors such as cytokine, chemokine, and growth factor activity, orchestrating the inflammatory and immune response. All of these characteristics make HMGB1 a critical molecular target in multiple human diseases including infectious diseases, ischemia, immune disorders, neurodegenerative diseases, metabolic disorders, and cancer. With regards to these various disease condition above, our review focus on the role of HMGB1 and CNS Diseases.

  19. High-mobility group box 1 protein and its role in severe acute pancreatitis

    Science.gov (United States)

    Shen, Xiao; Li, Wei-Qin

    2015-01-01

    The high mobility group box 1 (HMGB1), which belongs to the subfamily of HMG-1/-2, is a highly conserved single peptide chain consisting of 215 amino acid residues with a molecular weight of approximately 24894 Da. HMGB1 is a ubiquitous nuclear protein in mammals and plays a vital role in inflammatory diseases. Acute pancreatitis is one of the most common causes of acute abdominal pain with a poor prognosis. Acute pancreatitis is an acute inflammatory process of the pancreas (duration of less than six months), for which the severe form is called severe acute pancreatitis (SAP). More and more studies have shown that HMGB1 has a bidirectional effect in the pathogenesis of SAP. Extracellular HMGB1 can aggravate the pancreatic inflammatory process, whereas intracellular HMGB1 has a protective effect against pancreatitis. The mechanism of HMGB1 is multiple, mainly through the nuclear factor-κB pathway. Receptors for advanced glycation end-products and toll-like receptors (TLR), especially TLR-2 and TLR-4, are two major types of receptors mediating the inflammatory process triggered by HMGB1 and may be also the main mediators in the pathogenesis of SAP. HMGB1 inhibitors, such as ethyl pyruvate, pyrrolidine dithiocarbamate and Scolopendra subspinipes mutilans, can decrease the level of extracellular HMGB1 and are the promising targets in the treatment of SAP. PMID:25663762

  20. Two high-mobility group box domains act together to underwind and kink DNA

    Energy Technology Data Exchange (ETDEWEB)

    Sánchez-Giraldo, R.; Acosta-Reyes, F. J. [Universitat Politecnica de Catalunya, 08028 Barcelona (Spain); Malarkey, C. S. [University of Colorado School of Medicine, Aurora, CO 80045 (United States); Saperas, N. [Universitat Politecnica de Catalunya, 08028 Barcelona (Spain); Churchill, M. E. A., E-mail: mair.churchill@ucdenver.edu [University of Colorado School of Medicine, Aurora, CO 80045 (United States); Campos, J. L., E-mail: mair.churchill@ucdenver.edu [Universitat Politecnica de Catalunya, 08028 Barcelona (Spain)

    2015-06-30

    The crystal structure of HMGB1 box A bound to an unmodified AT-rich DNA fragment is reported at a resolution of 2 Å. A new mode of DNA recognition for HMG box proteins is found in which two box A domains bind in an unusual configuration generating a highly kinked DNA structure. High-mobility group protein 1 (HMGB1) is an essential and ubiquitous DNA architectural factor that influences a myriad of cellular processes. HMGB1 contains two DNA-binding domains, box A and box B, which have little sequence specificity but have remarkable abilities to underwind and bend DNA. Although HMGB1 box A is thought to be responsible for the majority of HMGB1–DNA interactions with pre-bent or kinked DNA, little is known about how it recognizes unmodified DNA. Here, the crystal structure of HMGB1 box A bound to an AT-rich DNA fragment is reported at a resolution of 2 Å. Two box A domains of HMGB1 collaborate in an unusual configuration in which the Phe37 residues of both domains stack together and intercalate the same CG base pair, generating highly kinked DNA. This represents a novel mode of DNA recognition for HMGB proteins and reveals a mechanism by which structure-specific HMG boxes kink linear DNA.

  1. Expression and Effects of High-Mobility Group Box 1 in Cervical Cancer

    Directory of Open Access Journals (Sweden)

    Xiaoao Pang

    2014-05-01

    Full Text Available We investigated the significance of high- mobility group box1 (HMGB1 and T-cell-mediated immunity and prognostic value in cervical cancer. HMGB1, forkhead/winged helix transcription factor p3 (Foxp3, IL-2, and IL-10 protein expression was analyzed in 100 cervical tissue samples including cervical cancer, cervical intraepithelial neoplasia (CIN, and healthy control samples using immunohistochemistry. Serum squamous cell carcinoma antigen (SCC-Ag was immunoradiometrically measured in 32 serum samples from 37 cases of squamous cervical cancer. HMGB1 and SCC-Ag were then correlated to clinicopathological characteristics. HMGB1 expression tends to increase as cervical cancer progresses and it was found to be significantly correlated to FIGO stage and lymph node metastasis. These findings suggest that HMGB1 may be a useful prognostic indicator of cervical carcinoma. In addition, there were significant positive relationships between HMGB1 and FOXP3 or IL-10 expression (both p < 0.05. In contrast, HMGB1 and IL-2 expression was negatively correlated (p < 0.05. HMGB1 expression may activate Tregs or facilitate Th2 polarization to promote immune evasion of cervical cancer. Elevated HMGB1 protein in cervical carcinoma samples was associated with a high recurrence of HPV infection in univariate analysis (p < 0.05. HMGB1 expression and levels of SCC-Ag were directly correlated in SCC (p < 0.05. Thus, HMGB1 may be a useful biomarker for patient prognosis and cervical cancer prediction and treatment.

  2. Charge transfer complexes of metal-free phthalocyanine radical anions with decamethylmetallocenium cations: (Cp*2Co+)(H2Pc˙-)·solvent and (Cp*2Cr+)(H2Pc˙-)·4C6H4Cl2.

    Science.gov (United States)

    Konarev, Dmitri V; Khasanov, Salavat S; Ishikawa, Manabu; Otsuka, Akihiro; Yamochi, Hideki; Saito, Gunzi; Lyubovskaya, Rimma N

    2017-03-14

    Charge transfer complexes (Cp*2Co+)(H2Pc˙-)·0.5C6H4Cl2·0.7C6H5CN·0.3C6H14 (1) and (Cp*2Cr+)(H2Pc˙-)·4C6H4Cl2 (2) have been obtained as single crystals. Both complexes contain metal-free phthalocyanine (Pc) radical anions and decamethylmetallocenium cations. Reduction of the Pc macrocycle leads to the appearance of new bands at 1026-1030 nm in the NIR range and blue shifts of both Soret and Q-bands of H2Pc in the spectra of 1 and 2. The geometry of the Pc macrocycles supports the formation of H2Pc˙- by the alternation of shorter and longer C-N(imine) bonds in the macrocycles in 2. Complex 1 contains pairs of H2Pc˙- having effective π-π interactions with two sandwiched Cp*2Co+ cations, whereas complex 2 contains stacks composed of alternating Cp*2Cr+ and H2Pc˙- ions. The magnetic moment of 1 is 1.64 μB at 300 K due to the contribution of the H2Pc˙- spins with the S = 1/2 state and diamagnetism of Cp*2Co+. This is supported by the observation of a narrow EPR signal of 1 with g = 2.0032-2.0036 characteristic of H2Pc˙-. Strong antiferromagnetic coupling of spins with a Weiss temperature of -23 K is observed between H2Pc˙- in 1. This coupling is probably mediated by the Cp*2Co+ cations. The magnetic moment of 2 is 4.18 μB at 300 K indicating the contribution of both paramagnetic H2Pc˙- (S = 1/2) and Cp*2Cr+ (S = 3/2) species. In spite of the presence of stacks of alternating ions in 2, only weak magnetic coupling is observed with a Weiss temperature of -4 K most probably due to ineffective π-π interactions between Cp*2Cr+ and H2Pc˙-. The EPR spectrum of 2 contains an asymmetric signal attributed to CrIII (g1 = 3.9059-3.9220) and a narrow Lorentzian signal from H2Pc˙- with g2 = 1.9943-1.9961. In addition to these signals, a broad EPR signal grows in intensity below 80 K with g4 = 2.1085-2.2438 which can be attributed to both paramagnetic Cp*2Cr+ and H2Pc˙- species having exchange interactions.

  3. Polyelectrolytes with sterically hindered anionic charges

    Energy Technology Data Exchange (ETDEWEB)

    Yeh, T.F.; Liu, H.; Okamoto, Y.; Lee, H.S.; Skotheim, T.A. (Polytechnic Inst. of Brooklyn, NY (USA); Brookhaven National Lab., Upton, NY (USA))

    1989-01-01

    The central problem in the development of single phase polymer electrolytes with exclusive cation conduction has been inadequate ion mobility due to extensive ion pairing between the mobile cation and the covalently attached anion. We have developed a new class of single ion conducting polymers, or polyelectrolytes, based on highly flexible polysiloxane backbones and attached sterically hindered phenolate anions. The combination of a highly delocalized and sterically enclosed anionic charged separation and consequently enhanced cation mobility. 10 refs., 2 figs.

  4. Ion-π interactions in ligand design for anions and main group cations.

    Science.gov (United States)

    Watt, Michelle M; Collins, Mary S; Johnson, Darren W

    2013-04-16

    /vis spectroscopy. Initial solution studies suggest these reversible interactions are weak in organic solvents, but the Hofmeister bias in anion binding could be mitigated, if not reversed, in the halides using these anion-π type interactions.

  5. Molecular-weight dependence of interchain polaron delocalization and exciton bandwidth in high-mobility conjugated polymers

    DEFF Research Database (Denmark)

    Chang, J.F.; Clark, J.; Zhao, N.

    2006-01-01

    here a detailed study of interchain interaction effects on both charged polarons as well as neutral excitons in highly crystalline, high-mobility poly-3-hexylthiophene (P3HT) as a function of molecular weight. We find experimental evidence for reduced exciton bandwidth and increased polaron...

  6. High mobility group box1 (HMGB1) in relation to cutaneous inflammation in systemic lupus erythematosus (SLE)

    NARCIS (Netherlands)

    Abdulahad, D. A.; Westra, J.; Reefman, E.; Zuidersma, E.; Bijzet, J.; Limburg, P. C.; Kallenberg, C. G. M.; Bijl, M.

    Photosensitivity is characteristic of systemic lupus erythematosus (SLE). Upon ultraviolet B (UVB) exposure, patients develop inflammatory skin lesions in the vicinity of sunburn cells (SBCs). High mobility group box 1 (HMGB1) is released from apoptotic and activated cells and exerts inflammatory

  7. High mobility group box1 (HMGB1) in relation to cutaneous inflammation in systemic lupus erythematosus (SLE)

    NARCIS (Netherlands)

    Abdulahad, D.A.; Westra, J.; Reefman, E.; Zuidersma, E.; Bijzet, J.; Limburg, P.C.; Kallenberg, C.G.M.; Bijl, M.

    2013-01-01

    Photosensitivity is characteristic of systemic lupus erythematosus (SLE). Upon ultraviolet B (UVB) exposure, patients develop inflammatory skin lesions in the vicinity of sunburn cells (SBCs). High mobility group box 1 (HMGB1) is released from apoptotic and activated cells and exerts inflammatory

  8. Interplay between human high mobility group protein 1 and replication protein A on psoralen-cross-linked DNA

    DEFF Research Database (Denmark)

    Reddy, Madhava C; Christensen, Jesper; Vasquez, Karen M

    2005-01-01

    Human high mobility group box (HMGB) 1 and -2 proteins are highly conserved and abundant chromosomal proteins that regulate chromatin structure and DNA metabolism. HMGB proteins bind preferentially to DNA that is bent or underwound and to DNA damaged by agents such as cisplatin, UVC radiation...

  9. Inhibition of high-mobility group box 1 as therapeutic option in autoimmune disease : lessons from animal models

    NARCIS (Netherlands)

    Schaper, Fleur; Heeringa, Peter; Bijl, Marc; Westra, Johanna

    Purpose of review High-mobility group box 1 (HMGB1) is a molecule that has gained much attention in the last couple of years as an important player in innate immune responses and modulating factor in several (auto) immune diseases. Furthermore, advancements have been made in identifying the diverse

  10. High-Mobility Aligned Pentacene Films Grown by Zone-Casting

    DEFF Research Database (Denmark)

    Duffy, Claudia M.; Andreasen, Jens Wenzel; Breiby, Dag W.

    2008-01-01

    We investigate the growth and field-effect transistor performance of aligned pentacene thin films deposited by zone-casting from a solution of unsubstituted pentacene molecules in a chlorinated solvent. Polarized optical microscopy shows that solution processed pentacene films grow as large...... devices depends strongly on the underlying dielectric. Divinylsiloxane-bis-benzocyclobutene (BCB) resin is found to be a suitable gate dielectric allowing reproducible film deposition and high field-effect mobilities up to 0.4−0.7 cm2/(V s) and on/off ratios of 106−107. A small mobility anisotropy...

  11. Organic solvents and cancer.

    Science.gov (United States)

    Lynge, E; Anttila, A; Hemminki, K

    1997-05-01

    Epidemiologic evidence on the relationship between organic solvents and cancer is reviewed. In the 1980s, more than a million persons were potentially exposed to some specific solvents in the United States; in Canada, 40 percent of male cancer patients in Montreal had experienced exposure to solvents; in the Finnish population, one percent was regularly exposed. There is evidence for increased risks of cancer following exposure to: trichloroethylene (for the liver and biliary tract and for non-Hodgkin's lymphomas); tetrachloroethylene (for the esophagus and cervix--although confounding by smoking, alcohol, and sexual habits cannot be excluded--and non-Hodgkin's lymphoma); and carbon tetrachloride (lymphohematopoietic malignancies). An excess risk of liver and biliary tract cancers was suggested in the cohort with the high exposure to methylene chloride, but not found in the other cohorts where an excess risk of pancreatic cancer was suggested. 1,1,1-trichloroethane has been used widely, but only a few studies have been done suggesting a risk of multiple myeloma. A causal association between exposure to benzene and an increased risk of leukemia is well-established, as well as a suggested risk of lung and nasopharynx cancer in a Chinese cohort. Increased risks of various gastrointestinal cancers have been suggested following exposure to toluene. Two informative studies indicated an increased risk of lung cancer, not supported by other studies. Increased risks of lymphohematopoietic malignancies have been reported in some studies of persons exposed to toluene or xylene, but not in the two most informative studies on toluene. Occupation as a painter has consistently been associated with a 40 percent increased risk of lung cancer. (With the mixed exposures, however, it is not possible to identify the specific causative agent[s].) A large number of studies of workers exposed to styrene have evidenced no consistent excess risk of all lymphohematopoietic malignancies

  12. Anionic and cationic Hofmeister effects on hydrophobic and hydrophilic surfaces.

    Science.gov (United States)

    Schwierz, Nadine; Horinek, Dominik; Netz, Roland R

    2013-02-26

    Using a two-step modeling approach, we address the full spectrum of direct, reversed, and altered ionic sequences as the charge of the ion, the charge of the surface, and the surface polarity are varied. From solvent-explicit molecular dynamics simulations, we extract single-ion surface interaction potentials for halide and alkali ions at hydrophilic and hydrophobic surfaces. These are used within Poisson-Boltzmann theory to calculate ion density and electrostatic potential distributions at mixed polar/unpolar surfaces for varying surface charge. The resulting interfacial tension increments agree quantitatively with experimental data and capture the Hofmeister series, especially the anomaly of lithium, which is difficult to obtain using continuum theory. Phase diagrams that feature different Hofmeister series as a function of surface charge, salt concentration, and surface polarity are constructed from the long-range force between two surfaces interacting across electrolyte solutions. Large anions such as iodide have a high hydrophobic surface affinity and increase the effective charge magnitude on negatively charged unpolar surfaces. Large cations such as cesium also have a large hydrophobic surface affinity and thereby compensate an external negative charge surface charge most efficiently, which explains the well-known asymmetry between cations and anions. On the hydrophilic surface, the size-dependence of the ion surface affinity is reversed, explaining the Hofmeister series reversal when comparing hydrophobic with hydrophilic surfaces.

  13. Perpendicularly Aligned, Anion Conducting Nanochannels in Block Copolymer Electrolyte Films

    Energy Technology Data Exchange (ETDEWEB)

    Arges, Christopher G.; Kambe, Yu; Suh, Hyo Seon; Ocola, Leonidas E.; Nealey, Paul F.

    2016-03-08

    Connecting structure and morphology to bulk transport properties, such as ionic conductivity, in nanostructured polymer electrolyte materials is a difficult proposition because of the challenge to precisely and accurately control order and the orientation of the ionic domains in such polymeric films. In this work, poly(styrene-block-2-vinylpyridine) (PSbP2VP) block copolymers were assembled perpendicularly to a substrate surface over large areas through chemical surface modification at the substrate and utilizing a versatile solvent vapor annealing (SVA) technique. After block copolymer assembly, a novel chemical vapor infiltration reaction (CVIR) technique selectively converted the 2-vinylpyridine block to 2-vinyl n-methylpyridinium (NMP+ X-) groups, which are anion charge carriers. The prepared block copolymer electrolytes maintained their orientation and ordered nanostructure upon the selective introduction of ion moieties into the P2VP block and post ion-exchange to other counterion forms (X- = chloride, hydroxide, etc.). The prepared block copolymer electrolyte films demonstrated high chloride ion conductivities, 45 mS cm(-1) at 20 degrees C in deionized water, the highest chloride ion conductivity for anion conducting polymer electrolyte films. Additionally, straight-line lamellae of block copolymer electrolytes were realized using chemoepitaxy and density multiplication. The devised scheme allowed for precise and accurate control of orientation of ionic domains in nanostructured polymer electrolyte films and enables a platform for future studies that examines the relationship between polymer electrolyte structure and ion transport.

  14. Role of high mobility group box 1 (HMGB1 in SCA17 pathogenesis.

    Directory of Open Access Journals (Sweden)

    Li-Ching Lee

    Full Text Available Spinocerebellar ataxia type 17 (SCA17 involves the expression of a polyglutamine (polyQ expanded TATA-binding protein (TBP, a general transcription initiation factor. TBP interacts with other protein factors, including high mobility group box 1 (HMGB1, to regulate gene expression. Previously, our proteomic analysis of soluble proteins prepared from mutant TBP (TBP/Q61 expressing cells revealed a reduced concentration of HMGB1. Here, we show that HMGB1 can be incorporated into mutant TBP aggregates, which leads to reduced soluble HMGB1 levels in TBP/Q(61∼79 expressing cells. HMGB1 overexpression reduced mutant TBP aggregation. HMGB1 cDNA and siRNA co-transfection, as well as an HSPA5 immunoblot and luciferase reporter assay demonstrated the important role of HMGB1 in the regulation of HSPA5 transcription. In starvation-stressed TBP/Q36 and TBP/Q79 cells, increased reactive oxygen species generation accelerated the cytoplasmic translocation of HMGB1, which accompanied autophagy activation. However, TBP/Q79 cells displayed a decrease in autophagy activation as a result of the reduction in the cytoplasmic HMGB1 level. In neuronal SH-SY5Y cells with induced TBP/Q(61∼79 expression, HMGB1 expression was reduced and accompanied by a significant reduction in the total outgrowth and branches in the TBP/Q(61∼79 expressing cells compared with the non-induced cells. The decreased soluble HMGB1 and impaired starvation-induced autophagy in cells suggest that HMGB1 may be a critical modulator of polyQ disease pathology and may represent a target for drug development.

  15. Autoantibodies to box A of high mobility group box 1 in systemic lupus erythematosus.

    Science.gov (United States)

    Schaper, F; de Leeuw, K; Horst, G; Maas, F; Bootsma, H; Heeringa, P; Limburg, P C; Westra, J

    2017-06-01

    Autoantibodies to nuclear structures are a hallmark of systemic lupus erythematosus (SLE), including autoantibodies to nuclear protein high mobility group box 1 (HMGB1). HMGB1 consists of three separate domains: box A, box B and an acidic tail. Recombinant box A acts as a competitive antagonist for HMGB1 and might be an interesting treatment option in SLE. However, antibodies to box A might interfere. Therefore, levels of anti-box A were examined in SLE patients in association with disease activity and clinical parameters. Serum anti-box A was measured in 86 SLE patients and 44 age- and sex-matched healthy controls (HC). Serum samples of 28 patients with primary Sjögren's syndrome and 32 patients with rheumatoid arthritis were included as disease controls. Anti-HMGB1 and anti-box B levels were also measured by enzyme-linked immunosorbent assay during quiescent disease [SLE Disease Activity Index (SLEDAI) ≤ 4, n = 47] and active disease (SLEDAI ≥ 5, n = 39). Anti-box A levels in active SLE patients were higher compared to quiescent patients, and were increased significantly compared to HC and disease controls. Anti-box A levels correlated positively with SLEDAI and anti-dsDNA levels and negatively with complement C3 levels. Increased levels of anti-box A antibodies were present in the majority of patients with nephritic (73%) and non-nephritic exacerbations (71%). Antibodies to the box A domain of HMGB1 might be an interesting new biomarker, as these had a high specificity for SLE and were associated with disease activity. Longitudinal studies should be performed to evaluate whether these antibodies perform better in predicting an exacerbation, especially non-nephritic exacerbations. © 2017 British Society for Immunology.

  16. High-mobility group protein B1: a new biomarker of metabolic syndrome in obese children.

    Science.gov (United States)

    Arrigo, Teresa; Chirico, Valeria; Salpietro, Vincenzo; Munafò, Caterina; Ferraù, Valeria; Gitto, Eloisa; Lacquaniti, Antonio; Salpietro, Carmelo

    2013-04-01

    Obesity is associated with a chronic low-grade inflammation. High-mobility group box 1 protein (HMGB1) plays a key role in inflammation and immunostimulatory and chemotactic processes. The aim of the study was to assess the role of HMGB1 in obese children and to evaluate its diagnostic profile in identifying childhood obesity-related complications, such as the metabolic syndrome (MS). Sixty obese children were enrolled and compared with 40 healthy children (control). Homeostasis model assessment of insulin resistance (HOMA-IR), lipid profile, thyroid hormones, and pro- and anti-inflammatory peptides such as C-reactive protein (CRP), adiponectin, interleukin 6 (IL6), IL18, IL23, TNFα, resistin, and HMGB1 were evaluated. Receiver operating characteristics (ROC) analysis was employed to calculate the area under the curve (AUC) for HMGB1, IL6, and adiponectin to find the best cutoff values capable of identifying MS in obese children. HMGB1 levels were statistically higher in obese patients than in the control group (19.4±6.8 vs 3.7±1.2 ng/ml; Pobese patients, IL18, IL6, and resistin levels were significantly high, while adiponectin levels were low. At multivariate analysis, HMGB1 was found to be independently correlated with BMI, IL23, IL6, free triiodothyronine, HDL, and HOMA-IR. At ROC analysis, HMGB1 showed higher sensitivity and specificity (AUC, 0. 992; sensitivity, 94.7%; specificity, 97.5%) than IL6 and adiponectin in identifying MS in obese children. HMGB1 plays an important role in the inflammatory process associated with childhood obesity. This peptide may be an important diagnostic marker for obesity-related complications, such as MS.

  17. High mobility group B1 impairs hepatocyte regeneration in acetaminophen hepatotoxicity

    Directory of Open Access Journals (Sweden)

    Yang Runkuan

    2012-05-01

    Full Text Available Abstract Background Acetaminophen (APAP overdose induces massive hepatocyte necrosis. Necrotic tissue releases high mobility group B1 (HMGB1, and HMGB1 contributes to liver injury. Even though blockade of HMGB1 does not protect against APAP-induced acute liver injury (ALI at 9 h time point, the later time points are not studied and the role of HMGB1 in APAP overdose is unknown, it is possible that neutralization of HMGB1 might improve hepatocyte regeneration. This study aims to test whether blockade of HMGB1 improves hepatocyte regeneration after APAP overdose. Methods Male C57BL/6 mice were treated with a single dose of APAP (350 mg/kg. 2 hrs after APAP administration, the APAP challenged mice were randomized to receive treatment with either anti-HMGB1 antibody (400 μg per dose or non-immune (sham IgG every 24 hours for a total of 2 doses. Results 24 hrs after APAP injection, anti-HMGB1 therapy instead of sham IgG therapy significantly improved hepatocyte regeneration microscopically; 48 hrs after APAP challenge, the sham IgG treated mice showed 14.6% hepatic necrosis; in contrast, blockade of HMGB1 significantly decreased serum transaminases (ALT and AST, markedly reduced the number of hepatic inflammatory cells infiltration and restored liver structure to nearly normal; this beneficial effect was associated with enhanced hepatic NF-κB DNA binding and increased the expression of cyclin D1, two important factors related to hepatocyte regeneration. Conclusion HMGB1 impairs hepatocyte regeneration after APAP overdose; Blockade of HMGB1 enhances liver recovery and may present a novel therapy to treat APAP overdose.

  18. Cardiac nuclear high mobility group box 1 prevents the development of cardiac hypertrophy and heart failure.

    Science.gov (United States)

    Funayama, Akira; Shishido, Tetsuro; Netsu, Shunsuke; Narumi, Taro; Kadowaki, Shinpei; Takahashi, Hiroki; Miyamoto, Takuya; Watanabe, Tetsu; Woo, Chang-Hoon; Abe, Jun-ichi; Kuwahara, Koichiro; Nakao, Kazuwa; Takeishi, Yasuchika; Kubota, Isao

    2013-09-01

    High mobility group box 1 (HMGB1) is an abundant and ubiquitous nuclear DNA-binding protein that has multiple functions dependent on its cellular location. HMGB1 binds to DNA, facilitating numerous nuclear functions including maintenance of genome stability, transcription, and repair. However, little is known about the effects of nuclear HMGB1 on cardiac hypertrophy and heart failure. The aim of this study was to examine whether nuclear HMGB1 plays a role in the development of cardiac hypertrophy induced by pressure overload. Analysis of human biopsy samples by immunohistochemistry showed decreased nuclear HMGB1 expression in failing hearts compared with normal hearts. Nuclear HMGB1 decreased in response to both endothelin-1 (ET-1) and angiotensin II (Ang II) stimulation in neonatal rat cardiomyocytes, where nuclear HMGB1 was acetylated and translocated to the cytoplasm. Overexpression of nuclear HMGB1 attenuated ET-1 induced cardiomyocyte hypertrophy. Thoracic transverse aortic constriction (TAC) was performed in transgenic mice with cardiac-specific overexpression of HMGB1 (HMGB1-Tg) and wild-type (WT) mice. Cardiac hypertrophy after TAC was attenuated in HMGB1-Tg mice and the survival rate after TAC was higher in HMGB1-Tg mice than in WT mice. Induction of foetal cardiac genes was decreased in HMGB1-Tg mice compared with WT mice. Nuclear HMGB1 expression was preserved in HMGB1-Tg mice compared with WT mice and significantly attenuated DNA damage after TAC was attenuated in HMGB1-TG mice. These results suggest that the maintenance of stable nuclear HMGB1 levels prevents hypertrophy and heart failure by inhibiting DNA damage.

  19. Urinary high-mobility group box-1 associates specifically with lupus nephritis class V.

    Science.gov (United States)

    Jog, N R; Blanco, I; Lee, I; Putterman, C; Caricchio, R

    2016-12-01

    High-mobility group box 1 protein (HMGB-1) has been implicated in the pathogenesis of lupus nephritis (LN). There is increased HMGB-1 expression in the kidneys and increased levels are observed in serum and urine of patients with LN. This study was performed to determine whether the increased urinary HMGB-1 was specific for active lupus or secondary to renal damage. Urine from 61 lupus patients (32 had active LN and 29 had systemic lupus erythematosus (SLE) with no evidence of LN) and 14 control proteinuric patients (all with hypertension and eight also with diabetes) were included in this study. HMGB-1 was detected by Western blot. Urine protein was normalized to urine creatinine to account for volume of the specimen. Median normalized urine HMGB-1 levels were significantly elevated in LN patients compared to lupus patients without kidney disease (53.81 vs 9.46, p classes, with a significant difference between proliferative and membranous disease (33.4 vs 138.8, p = 0.003). Urine protein to urine creatinine ratio (P/C) correlated with urinary HMGB-1 (r = 0.52, p classes this was true only for membranous disease (r = 0.71, p = 0.022, proliferative, p = 0.63; mixed, p = 0.34). HMGB-1 is elevated in the urine of patients with active LN. Levels are associated with LN class, and higher levels of urinary HMGB-1 are seen in patients with class V when compared to both proliferative and mixed classes. Therefore, urinary HMGB-1 may be suggestive of membranous LN and warrants further evaluation in a large lupus cohort. © The Author(s) 2016.

  20. Observation of a distinct surface molecular orientation in films of a high mobility conjugated polymer.

    Science.gov (United States)

    Schuettfort, Torben; Thomsen, Lars; McNeill, Christopher R

    2013-01-23

    The molecular orientation and microstructure of films of the high-mobility semiconducting polymer poly(N,N-bis-2-octyldodecylnaphthalene-1,4,5,8-bis-dicarboximide-2,6-diyl-alt-5,5-2,2-bithiophene) (P(NDI2OD-T2)) are probed using a combination of grazing-incidence wide-angle X-ray scattering (GIWAXS) and near-edge X-ray absorption fine-structure (NEXAFS) spectroscopy. In particular a novel approach is used whereby the bulk molecular orientation and surface molecular orientation are simultaneously measured on the same sample using NEXAFS spectroscopy in an angle-resolved transmission experiment. Furthermore, the acquisition of bulk-sensitive NEXAFS data enables a direct comparison of the information provided by GIWAXS and NEXAFS. By comparison of the bulk-sensitive and surface-sensitive NEXAFS data, a distinctly different molecular orientation is observed at the surface of the film compared to the bulk. While a more "face-on" orientation of the conjugated backbone is observed in the bulk of the film, consistent with the lamella orientation observed by GIWAXS, a more "edge-on" orientation is observed at the surface of the film with surface-sensitive NEXAFS spectroscopy. This distinct edge-on surface orientation explains the high in-plane mobility that is achieved in top-gate P(NDI2OD-T2) field-effect transistors (FETs), while the bulk face-on texture explains the high out-of-plane mobilities that are observed in time-of-flight and diode measurements. These results also stress that GIWAXS lacks the surface sensitivity required to probe the microstructure of the accumulation layer that supports charge transport in organic FETs and hence may not necessarily be appropriate for correlating film microstructure and FET charge transport.

  1. High Mobility Group A2 protects cancer cells against telomere dysfunction

    Science.gov (United States)

    Natarajan, Suchitra; Begum, Farhana; Gim, Jeonga; Wark, Landon; Henderson, Dana; Davie, James R.

    2016-01-01

    The non-histone chromatin binding protein High Mobility Group AT-hook protein 2 (HMGA2) plays important roles in the repair and protection of genomic DNA in embryonic stem cells and cancer cells. Here we show that HMGA2 localizes to mammalian telomeres and enhances telomere stability in cancer cells. We present a novel interaction of HMGA2 with the key shelterin protein TRF2. We found that the linker (L1) region of HMGA2 contributes to this interaction but the ATI-L1-ATII molecular region of HMGA2 is required for strong interaction with TRF2. This interaction was independent of HMGA2 DNA-binding and did not require the TRF2 interacting partner RAP1 but involved the homodimerization and hinge regions of TRF2. HMGA2 retained TRF2 at telomeres and reduced telomere-dysfunction despite induced telomere stress. Silencing of HMGA2 resulted in (i) reduced binding of TRF2 to telomere DNA as observed by ChIP, (ii) increased telomere instability and (iii) the formation of telomere dysfunction-induced foci (TIF). This resulted in increased telomere aggregation, anaphase bridges and micronuclei. HMGA2 prevented ATM-dependent pTRF2T188 phosphorylation and attenuated signaling via the telomere specific ATM-CHK2-CDC25C DNA damage signaling axis. In summary, our data demonstrate a unique and novel role of HMGA2 in telomere protection and promoting telomere stability in cancer cells. This identifies HMGA2 as a new therapeutic target for the destabilization of telomeres in HMGA2+ cancer cells. PMID:26799419

  2. High mobility group box 1-induced epithelial mesenchymal transition in human airway epithelial cells.

    Science.gov (United States)

    Chen, Yu-Ching; Statt, Sarah; Wu, Reen; Chang, Hao-Teng; Liao, Jiunn-Wang; Wang, Chien-Neng; Shyu, Woei-Cherng; Lee, Chen-Chen

    2016-01-07

    Epithelial-mesenchymal transition (EMT) is implicated in bronchial remodeling and loss of lung function in chronic inflammatory airway diseases. Previous studies showed the involvement of the high mobility group box 1 (HMGB1) protein in the pathology of chronic pulmonary inflammatory diseases. However, the role of HMGB1 in EMT of human airway epithelial cells is still unclear. In this study, we used RNA sequencing to show that HMGB1 treatment regulated EMT-related gene expression in human primary-airway epithelial cells. The top five upregulated genes were SNAI2, FGFBP1, VIM, SPARC (osteonectin), and SERPINE1, while the downregulated genes included OCLN, TJP1 (ZO-1), FZD7, CDH1 (E-cadherin), and LAMA5. We found that HMGB1 induced downregulation of E-cadherin and ZO-1, and upregulation of vimentin mRNA transcription and protein translation in a dose-dependent manner. Additionally, we observed that HMGB1 induced AKT phosphorylation, resulting in GSK3β inactivation, cytoplasmic accumulation, and nuclear translocation of β-catenin to induce EMT in human airway epithelial cells. Treatment with PI3K inhibitor (LY294006) and β-catenin shRNA reversed HMGB1-induced EMT. Moreover, HMGB1 induced expression of receptor for advanced glycation products (RAGE), but not that of Toll-like receptor (TLR) 2 or TLR4, and RAGE shRNA inhibited HMGB1-induced EMT in human airway epithelial cells. In conclusion, we found that HMGB1 induced EMT through RAGE and the PI3K/AKT/GSK3β/β-catenin signaling pathway.

  3. Porphyromonas Gingivalis Elevated High-Mobility Group Box 1 Levels After Myocardial Infarction in Mice.

    Science.gov (United States)

    Srisuwantha, Rungtiwa; Shiheido, Yuka; Aoyama, Norio; Sato, Hiroki; Kure, Keitetsu; Laosrisin, Narongsak; Izumi, Yuichi; Suzuki, Jun-Ichi

    2017-10-21

    High mobility group box 1 (HMGB1) is a nuclear protein released from necrotic cells, inducing inflammatory responses. Epidemiological studies suggested a possible association between periodontitis and cardiovascular diseases (CVDs). Due to tissue damage and necrosis of cardiac cells following myocardial infarction (MI), HMGB1 is released, activating an inflammatory reaction. However, it remains unclear whether periodontitis is also involved in myocardial damage. The purpose of this study was to determine the effect of the periodontal pathogen Porphyromonas gingivalis (P.g.) after MI in mice.C57BL/6J wild type mice in post-MI were inoculated with P.g. in the infected group (P.g.-inoculated MI group) and with phosphate buffer saline (PBS) in the control group (PBS-injected MI group). Plasma samples and twelve tissue samples from mice hearts after MI were obtained. We determined the expression of HMGB1 by ELISA and immunohistochemistry.The level of HMGB1 protein in the P.g.-inoculated MI group was significantly higher than in the PBS-injected MI group on day 5, but not on day 14. Immunohistochemistry analysis revealed that HMGB1 was mainly expressed in cardiomyocytes, immune cells, and vascular endothelial cells in the PBS-injected MI group, while HMGB1 was seen broadly in degenerated cardiomyocytes, extracellular fields, immune cells, and vascular endothelial cells in the P.g.-inoculated MI group. A significant increase in the number of HMGB1 positive cells was observed in the P.g.-inoculated MI group compared to the PBS-injected MI group.Infection with P.g. after MI enhanced myocardial HMGB1 expression. There is a possible relationship between periodontitis and post-infarction myocardial inflammation through HMGB-1.

  4. Solvent effects in chemistry

    CERN Document Server

    Buncel, Erwin

    2015-01-01

    This book introduces the concepts, theory and experimental knowledge concerning solvent effects on the rate and equilibrium of chemical reactions of all kinds.  It begins with basic thermodynamics and kinetics, building on this foundation to demonstrate how a more detailed understanding of these effects may be used to aid in determination of reaction mechanisms, and to aid in planning syntheses. Consideration is given to theoretical calculations (quantum chemistry, molecular dynamics, etc.), to statistical methods (chemometrics), and to modern day concerns such as ""green"" chemistry, where ut

  5. The paradox of hydrogen-bonded anion-anion aggregates in oxoanions: a fundamental electrostatic problem explained in terms of electrophilic···nucleophilic interactions.

    Science.gov (United States)

    Mata, Ignasi; Molins, Elies; Alkorta, Ibon; Espinosa, Enrique

    2015-01-08

    A theoretical study of anionic complexes formed by two partly deprotonated oxoacids joined by hydrogen bonds has been carried out at the MP2 computational level. In spite of the ionic repulsion, local energy minima are found both in the gas phase and in aqueous solution. Electrostatic potential and electron density topologies, and the comparison with neutral complexes formed by oxoacids, reveal that the ionization has no significant effect on the properties of the hydrogen bonds. The stability of the complexes in the gas phase is explained by attractive forces localized in a volume situated in the hydrogen bond and defined as the electrostatic attraction region (EAR) and determined by the topological analyses of the electron density and the electrostatic potential, and by the electric field lines. In solution, the strong anionic repulsion is mostly screened by the effect of the surrounding polar solvent, which only leads to a weak destabilizing interaction in the hydrogen bond region and finally favors the overall stability of the complexes. The anion-anion complexes have been compared with the corresponding neutral ones (as salts or protonated forms), showing that EAR remains unchanged along the series.

  6. Tripodal Receptors for Cation and Anion Sensors

    Directory of Open Access Journals (Sweden)

    David N. Reinhoudt

    2006-08-01

    Full Text Available 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 are emphasised, along with their potential applications in optical sensors or optodes.

  7. Neutral anion receptors: design and application

    NARCIS (Netherlands)

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

    1998-01-01

    After the development of synthetic cation receptors in the late 1960s, only in the past decade has work started on the development of synthetic neutral anion receptors. Combination and preorganization of different anion binding groups, like amides, urea moieties, or Lewis acidic metal centers lead

  8. Gels based on anion recognition between triurea receptor and phosphate anion.

    Science.gov (United States)

    Yang, Cuiling; Wu, Biao; Chen, Yongming; Zhang, Ke

    2015-04-01

    Anion recognition between the triurea receptor and phosphate anion is demonstrated as the cross-linkage to build supramolecular polymer gels for the first time. A novel multi-block copolymer (3) is designed to have functional triurea groups as cross-linking units along the polymer main chain. By virtue of anion coordination between the triurea receptor and phosphate anion with a binding mode of 2:1, supramolecular polymer gels are then prepared based on anion recognition using 3 as the building block. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. 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.

  10. Fungal growth on anion surfactant medium.

    Science.gov (United States)

    Hamada, Nobuo; Abe, Niichiro

    2009-12-01

    Before the present study, no fungi using anion surfactant as a nutrient had been identified, although some fungi were known to use nonion surfactant. Washing water collected from 63 washing machines was inoculated onto 0.1% LAS (Sodium dodecyl benzenesulfonate) anion surfactant media to identify fungi that can feed on anion-surfactant. Small dark colonies of fungi were found on several of the Petri-dishes from 12 days after inoculation. These were identified as Cladophialophora boppii and Exophiala spinifera using morphological features and rDNA data. A number of the isolates of C. boppii specifically were recognized as using anion surfactant as a nutrient. The growth characteristics of the two fungal species were examined on surfactant media of three kinds. Apart from anion surfactant, the fungi were also able to grow on nonion surfactant and on soap. The application of these fungi for environmental cleansing after detergent pollution is also discussed.

  11. 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.

  12. Solvent extraction: the coordination chemistry behind extractive metallurgy.

    Science.gov (United States)

    Wilson, A Matthew; Bailey, Phillip J; Tasker, Peter A; Turkington, Jennifer R; Grant, Richard A; Love, Jason B

    2014-01-07

    The modes of action of the commercial solvent extractants used in extractive hydrometallurgy are classified according to whether the recovery process involves the transport of metal cations, M(n+), metalate anions, MXx(n-), or metal salts, MXx into a water-immiscible solvent. Well-established principles of coordination chemistry provide an explanation for the remarkable strengths and selectivities shown by most of these extractants. Reagents which achieve high selectivity when transporting metal cations or metal salts into a water-immiscible solvent usually operate in the inner coordination sphere of the metal and provide donor atom types or dispositions which favour the formation of particularly stable neutral complexes that have high solubility in the hydrocarbons commonly used in recovery processes. In the extraction of metalates, the structures of the neutral assemblies formed in the water-immiscible phase are usually not well defined and the cationic reagents can be assumed to operate in the outer coordination spheres. The formation of secondary bonds in the outer sphere using, for example, electrostatic or H-bonding interactions are favoured by the low polarity of the water-immiscible solvents.

  13. Solvent effects and chemical reactivity

    National Research Council Canada - National Science Library

    Tapia, Orlando; Bertrán, J

    1996-01-01

    ... original contributions from a selected group of distinguished researchers that are actively working in the theory and practical applications of solvent effects and chemical reactions. The importance...

  14. Toll-like receptor 4 mediates acute lung injury induced by high mobility group box-1.

    Directory of Open Access Journals (Sweden)

    Yuxiao Deng

    Full Text Available BACKGROUND: Acute lung injury (ALI is considered to be the major cause of respiratory failure in critically ill patients. Clinical studies have found that in patients with sepsis and after hemorrhage, the elevated level of high mobility group box-1(HMGB-1 in their circulation is highly associated with ALI, but the underlying mechanism remains unclear. Extracellular HMGB-1 has cytokine-like properties and can bind to Toll-like Receptor-4 (TLR4, which was reported to play an important role in the pathogenesis of ALI. The aim of this study was to determine whether HMGB-1 directly contributes to ALI and whether TLR4 signaling pathway is involved in this process. METHODS: Recombinant human HMGB-1 (rhHMGB-1 was used to induce ALI in male Sprague-Dawley rats. Lung specimens were collected 2 h after HMGB-1 treatment. The levels of TNF-α, IL-1β, TLR4 protein, and TLR4 mRNA in lungs as well as pathological changes of lung tissue were assessed. In cell studies, the alveolar macrophage cell line, NR8383, was collected 24 h after rhHMGB-1 treatment and the levels of TNF-α and IL-1β in cultured medium as well as TLR4 protein and mRNA levels in the cell were examined. TLR4-shRNA-lentivirus was used to inhibit TLR4 expression, and a neutralizing anti-HMGB1 antibody was used to neutralize rhHMGB-1 both in vitro and in vivo. RESULTS: Features of lung injury and significant elevation of IL-1β and TNF-α levels were found in lungs of rhHMGB-1-treated animals. Cultured NR8383 cells were activated by rhHMGB-1 treatment and resulted in the release of IL-1β and TNF-α. TLR4 expression was greatly up-regulated by rhHMGB-1. Inhibition of TLR4 or neutralization of HMGB1 with a specific antibody also attenuated the inflammatory response induced by HMGB-1 both in vivo and in vitro. CONCLUSION: HMGB-1 can activate alveolar macrophages to produce proinflammatory cytokines and induce ALI through a mechanism that relies on TLR-4.

  15. High mobility group-box 3 overexpression is associated with poor prognosis of resected gastric adenocarcinoma.

    Science.gov (United States)

    Tang, Hua-Rong; Luo, Xian-Qin; Xu, Gang; Wang, Yan; Feng, Zhi-Jun; Xu, Hui; Shi, Ya-Wei; Zhang, Qin; Wu, Li-Guang; Xue, Chun-Quan; Wang, Cheng-Wei; Wu, Chao-Yang

    2012-12-28

    To elucidate high mobility group-box 3 (HMGB3) protein expression in gastric adenocarcinoma, its potential prognostic relevance, and possible mechanism of action. Ninety-two patients with gastric adenocarcinomas surgically removed entered the study. HMGB3 expression was determined by immunohistochemistry through a tissue microarray procedure. The clinicopathologic characteristics of all patients were recorded, and regular follow-up was made for all patients. The inter-relationship of HMGB3 expression with histological and clinical factors was analyzed using nonparametric tests. Survival analysis was carried out by Kaplan-Meier (log-rank) and multivariate Cox (Forward LR) analyses between the group with overexpression of HMGB3 and the group with low or no HMGB3 expression to determine the prognosis value of HMGB3 expression on overall survival. Further, HMGB3 expression was knocked down by small hairpin RNAs (shRNAs) in the human gastric cancer cell line BGC823 to observe its influence on cell biological characteristics. The MTT method was utilized to detect gastric cancer cell proliferation changes, and cell cycle distribution was analyzed by flow cytometry. Among 92 patients with gastric adenocarcinomas surgically removed in this study, high HMGB3 protein expression was detected in the gastric adenocarcinoma tissues vs peritumoral tissues (P hazard ratio = 2.791, 95%CI = 1.233-6.319, P = 0.019). In the gene function study, after HMGB3 was knocked down in the gastric cell line BGC823 by shRNA, the cell proliferation rate was reduced at 24 h, 48 h and 72 h. Compared to BGC823 shRNA-negative control (NC) cells, the cell proliferation rate in cells that had HMGB3 shRNA transfected was significantly decreased (P < 0.01). Finally, cell cycle analysis by FACS showed that BGC823 cells that had HMGB3 knocked down were blocked in G1/G0 phase. The percentage of cells in G1/G0 phase in BGC823 cells with shRNA-NC and with shRNA-HMGB3 was 46.84% ± 1.7%, and 73.03% ± 3

  16. High-mobility three-atom-thick semiconducting films with wafer-scale homogeneity.

    Science.gov (United States)

    Kang, Kibum; Xie, Saien; Huang, Lujie; Han, Yimo; Huang, Pinshane Y; Mak, Kin Fai; Kim, Cheol-Joo; Muller, David; Park, Jiwoong

    2015-04-30

    The large-scale growth of semiconducting thin films forms the basis of modern electronics and optoelectronics. A decrease in film thickness to the ultimate limit of the atomic, sub-nanometre length scale, a difficult limit for traditional semiconductors (such as Si and GaAs), would bring wide benefits for applications in ultrathin and flexible electronics, photovoltaics and display technology. For this, transition-metal dichalcogenides (TMDs), which can form stable three-atom-thick monolayers, provide ideal semiconducting materials with high electrical carrier mobility, and their large-scale growth on insulating substrates would enable the batch fabrication of atomically thin high-performance transistors and photodetectors on a technologically relevant scale without film transfer. In addition, their unique electronic band structures provide novel ways of enhancing the functionalities of such devices, including the large excitonic effect, bandgap modulation, indirect-to-direct bandgap transition, piezoelectricity and valleytronics. However, the large-scale growth of monolayer TMD films with spatial homogeneity and high electrical performance remains an unsolved challenge. Here we report the preparation of high-mobility 4-inch wafer-scale films of monolayer molybdenum disulphide (MoS2) and tungsten disulphide, grown directly on insulating SiO2 substrates, with excellent spatial homogeneity over the entire films. They are grown with a newly developed, metal-organic chemical vapour deposition technique, and show high electrical performance, including an electron mobility of 30 cm(2) V(-1) s(-1) at room temperature and 114 cm(2) V(-1) s(-1) at 90 K for MoS2, with little dependence on position or channel length. With the use of these films we successfully demonstrate the wafer-scale batch fabrication of high-performance monolayer MoS2 field-effect transistors with a 99% device yield and the multi-level fabrication of vertically stacked transistor devices for three

  17. Retinol-induced changes in the phosphorylation levels of histones and high mobility group proteins from Sertoli cells

    Directory of Open Access Journals (Sweden)

    J.C.F. Moreira

    2000-03-01

    Full Text Available Chromatin proteins play a role in the organization and functions of DNA. Covalent modifications of nuclear proteins modulate their interactions with DNA sequences and are probably one of the multiple factors involved in the process of switch on/off transcriptionally active regions of DNA. Histones and high mobility group proteins (HMG are subject to many covalent modifications that may modulate their capacity to bind to DNA. We investigated the changes induced in the phosphorylation pattern of cultured Wistar rat Sertoli cell histones and high mobility group protein subfamilies exposed to 7 µM retinol for up to 48 h. In each experiment, 6 h before the end of the retinol treatment each culture flask received 370 KBq/ml [32P]-phosphate. The histone and HMGs were isolated as previously described [Moreira et al. Medical Science Research (1994 22: 783-784]. The total protein obtained by either method was quantified and electrophoresed as described by Spiker [Analytical Biochemistry (1980 108: 263-265]. The gels were stained with Coomassie brilliant blue R-250 and the stained bands were cut and dissolved in 0.5 ml 30% H2O2 at 60oC for 12 h. The vials were chilled and 5.0 ml scintillation liquid was added. The radioactivity in each vial was determined with a liquid scintillation counter. Retinol treatment significantly changed the pattern of each subfamily of histone and high mobility group proteins.

  18. Thin Film Transistor Gas Sensors Incorporating High-Mobility Diketopyrrolopyrole-Based Polymeric Semiconductor Doped with Graphene Oxide.

    Science.gov (United States)

    Cheon, Kwang Hee; Cho, Jangwhan; Kim, Yun-Hi; Chung, Dae Sung

    2015-07-01

    In this work, we fabricated a diketopyrrolopyrole-based donor-acceptor copolymer composite film. This is a high-mobility semiconductor component with a functionalized-graphene-oxide (GO) gas-adsorbing dopant, used as an active layer in gas-sensing organic-field-effect transistor (OFET) devices. The GO content of the composite film was carefully controlled so that the crystalline orientation of the semiconducting polymer could be conserved, without compromising its gas-adsorbing ability. The resulting optimized device exhibited high mobility (>1 cm(2) V(-1) s(-1)) and revealed sensitive response during programmed exposure to various polar organic molecules (i.e., ethanol, acetone, and acetonitrile). This can be attributed to the high mobility of polymeric semiconductors, and also to their high surface-to-volume ratio of GO. The operating mechanism of the gas sensing GO-OFET is fully discussed in conjunction with charge-carrier trap theory. It was found that each transistor parameter (e.g., mobility, threshold voltage), responds independently to each gas molecule, which enables high selectivity of GO-OFETs for various gases. Furthermore, we also demonstrated practical GO-OFET devices that operated at low voltage (<1.5 V), and which successfully responded to gas exposure.

  19. Brønsted acid-catalyzed α-halogenation of ynamides from halogenated solvents and pyridine-N-oxides.

    Science.gov (United States)

    Kim, Seung Woo; Um, Tae-Woong; Shin, Seunghoon

    2017-02-28

    The keteniminium ions generated from the protonation of ynamides formed reversible adducts with counter anions and pyridine-N-oxides as well as halogenated solvents. Above 80 °C, the halonium ions selectively undergo a rate-limiting attack by pyridine-N-oxides, leading to (E)-haloenamides in good yields.

  20. Non-covalent synthesis of calix[4]arene-capped porphyrins in polar solvents via ionic interactions

    NARCIS (Netherlands)

    Fiammengo, R.; Timmerman, P.; Huskens, Jurriaan; Versluis, Kees; Heck, Albert J.R.; Reinhoudt, David

    2002-01-01

    Non-covalent synthesis of calix[4]arene capped porphyrins can be achieved in polar solvents (up to 45% molar fraction of water) via ionic interaction. Thus tetracationic meso-tetrakis(N-alkylpyridinium-3-yl) porphyrins 1a–d and tetra anionic 25,26,27,28-tetrakis(2-ethoxyethoxy)-calix[4]arene

  1. 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...

  2. Solvent Induced Conformational Kinetics (SICK)

    NARCIS (Netherlands)

    Jonkman, Leffert; Kommandeur, Jan

    1970-01-01

    Specific conformations of molecules may be induced by the solvent when a large free volume is associated with the oonformational change. The conformational energy barrier is then a property of the solvent, rather than of the molecule. Such effects are reported for several substituted

  3. SOLVENT EXTRACTION OF URANIUM VALUES

    Science.gov (United States)

    Feder, H.M.; Ader, M.; Ross, L.E.

    1959-02-01

    A process is presented for extracting uranium salt from aqueous acidic solutions by organic solvent extraction. It consists in contacting the uranium bearing solution with a water immiscible dialkylacetamide having at least 8 carbon atoms in the molecule. Mentioned as a preferred extractant is dibutylacetamide. The organic solvent is usually used with a diluent such as kerosene or CCl/sub 4/.

  4. Microsolvation of anions by molecules forming CH··X{sup −} hydrogen bonds

    Energy Technology Data Exchange (ETDEWEB)

    Nepal, Binod; Scheiner, Steve, E-mail: steve.scheiner@usu.edu

    2015-12-16

    Highlights: • n CF{sub 3}H + anion forms clusters with n CH···X{sup −} H-bonds. • F{sup −}, Cl{sup −}, Br{sup −}, I{sup −}, CN{sup −}, NO{sub 3}{sup −}, HCOO{sup −}, CH{sub 3}COO{sup −}, HSO{sub 4}{sup −}, H{sub 2}PO{sub 4}{sup −}, SO{sub 4}{sup 2−}, HPO{sub 4}{sup 2−}, PO{sub 4}{sup 3−}. • Average H-bond energy decreases steadily with n as average R increases. • Total binding energies proportional to the magnitude of the anionic charge. - Abstract: Various anions were surrounded by n molecules of CF{sub 3}H, which was used as a prototype CH donor solvent, and the structures and energies studied by M06-2X calculations with a 6-31+G∗∗ basis set. Anions considered included the halides F{sup −}, Cl{sup −}, Br{sup −} and I{sup −}, as well as those with multiple proton acceptor sites: CN{sup −}, NO{sub 3}{sup −}, HCOO{sup −}, CH{sub 3}COO{sup −}, HSO{sub 4}{sup −}, H{sub 2}PO{sub 4}{sup −}, and anions with higher charges SO{sub 4}{sup 2−}, HPO{sub 4}{sup 2−} and PO{sub 4}{sup 3−}. Well structured cages were formed and the average H-bond energy decreases steadily as the number of surrounding solvent molecules rises, even when n exceeds 6 and the CF{sub 3}H molecules begin to interact with one another rather than with the central anion. Total binding energies are very nearly proportional to the magnitude of the negative charge on the anion. The free energy of complexation becomes more negative for larger n initially, but then reaches a minimum and begins to rise for larger values of n.

  5. Enzymatic Synthesis of Esculin Ester in Ionic Liquids Buffered with Organic Solvents

    DEFF Research Database (Denmark)

    Hu, Yifan; Guo, Zheng; Lue, Bena-Marie

    2009-01-01

    The enzymatic esterification of esculin catalyzed by Candida antarctica lipase B (Novozym 435) was carried out in ionic liquid (IL)-organic solvent mixed systems in comparison with individual systems. The reaction behaviors in IL-organic solvents were systemically evaluated using acetone as a model...... in IL-acetone mixtures made it possible to improve the solubility of esculin while the effects of ILs on lipase activity were minimized. Following the benignity of ILs to lipase activity, the anions of ILs were ranked in the order as [Tf2N](-) > [PF6](-) > [BF4](-) > [CF3SO3](-) > [C4F9SO3](-) > [TAF...

  6. A nanostarch functionalized ionic liquid containing imidazolium cation and cobalt chelate anion for the synthesis of carbamates from amines and dimethyl carbonate.

    Science.gov (United States)

    Kumar, Subodh; Jain, Suman L

    2013-11-14

    A new nanostarch functionalized ionic liquid containing imidazolium cation and cobalt chelate anion was synthesized and tested for the one pot synthesis of carbamates by the reaction of amines and dimethyl carbonate (DMC), affording excellent yield of the products under solvent free mild reaction conditions. The synthesized ionic liquid was easily recovered and reused several times without any loss in catalytic efficiency.

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

    Science.gov (United States)

    2015-01-15

    using Friedel−Crafts alkylation chemistry .15 Recently, Wang and Hickner reported low-temperature cross-linking of styrene-based copolymers with pendent...Diffusion at Infinite Dilution. In CRC Handbook of Chemistry and Physics, 81st ed.; CRC Press: Boca Raton, FL, 2001. (34) Schmidt-Rohr, K.; Chen, Q. Nat...5390− 5397. (37) Beers , K. M.; Balsara, N. P. ACS Macro Lett. 2012, 1, 1155− 1160. (38) Marino, M. G.; Melchior, J. P.; Wohlfarth, A.; Kreuer, K. D

  8. Selective Nitrate Binding in Competitive Hydrogen Bonding Solvents: Do Anion–π Interactions Facilitate Nitrate Selectivity?**

    Science.gov (United States)

    Watt, Michelle M.; Zakharov, Lev N.

    2013-01-01

    New tripodal urea receptors demonstrate preferential binding of anions over competitive hydrogen bonding solvents. 1H NMR titrations in 10% DMSO-d6/CDCl3 show a higher affinity for nitrate over the halides for the fluorinated receptor, which is lost when the fluorines are removed. An “anion–π” interaction between the nitrate and the π-system of the ethynyl-substituted arene is proposed as the source of this selectivity. PMID:23939999

  9. Azocalixarene. 5: p-Substituted Azocalix4arenes as Extractants for Dichromate Anions

    Directory of Open Access Journals (Sweden)

    Hasalettin Deligöz

    2008-06-01

    Full Text Available In this article, chromium(VI extraction properties of two azocalix4arene based receptors (L4 and L6 are reported. A preliminary evaluation of the binding efficiencies of p-substituted azocalix4arene derivatives L4 and L6 was carried out by solvent extraction of Na-dichromate from aqueous solution into dichloromethane at different pH. It was observed that the new compounds are effective extractants for transferring the HCr2O7-/Cr2O72- anions at low pH. The binding ability of these compounds toward HCr2O7-/Cr2O72- anions depends upon Na+ extraction.

  10. Photoluminescence from Amino-Containing Polymer in the Presence of CO2: Carbamato Anion Formed as a Fluorophore

    Science.gov (United States)

    Pan, Xiaoyong; Wang, Guan; Lay, Chee Leng; Tan, Beng Hong; He, Chaobin; Liu, Ye

    2013-01-01

    Organic photoluminescent materials are important to many applications especially for diagnosis and detection, and most of organic photoluminescent materials contain fluorophores with extended conjugated structures. Recently some of amino-containing polymers without fluorophores with extended conjugated structure are observed to be photoluminescent, and one possible cause of the photoluminescence is oxidation of the amines. Here we show that photoluminescence can be produced by exposing a typical amino-containing polymer, polyethylenimine, to carbon dioxide. We demonstrate that carbamato anion formed via the reaction between the amine and carbon dioxide is a fluorophore; and the loosely-bound protonated water molecule can increase UV absorption but reduce the photoluminescence emission. Also carbamato anion shows solvent- and excitation wavelength-dependent emission of photoluminescence. The photoluminescence profile of carbamoto anion was discussed. These results will facilitate the understanding of photoluminescence observed from amino-containing materials and the design of new fluorophores. PMID:24067377

  11. Selection and design of solvents

    DEFF Research Database (Denmark)

    Gani, Rafiqul

    and design of solvents will be presented together with application examples. The selection problem is defined as finding known chemicals that match the desired functions of a solvent for a specified set of applications. The design problem is defined as finding the molecular structure (or mixture of molecules....... With increasing interest on issues such as waste, sustainability, environmental impact and green chemistry, the selection and design of solvents have become important problems that need to be addressed during chemical product-process design and development. Systematic methods and tools suitable for selection...

  12. Acetone-based cellulose solvent.

    Science.gov (United States)

    Kostag, Marc; Liebert, Tim; Heinze, Thomas

    2014-08-01

    Acetone containing tetraalkylammonium chloride is found to be an efficient solvent for cellulose. The addition of an amount of 10 mol% (based on acetone) of well-soluble salt triethyloctylammonium chloride (Et3 OctN Cl) adjusts the solvent's properties (increases the polarity) to promote cellulose dissolution. Cellulose solutions in acetone/Et3 OctN Cl have the lowest viscosity reported for comparable aprotic solutions making it a promising system for shaping processes and homogeneous chemical modification of the biopolymer. Recovery of the polymer and recycling of the solvent components can be easily achieved. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Handbook of organic solvent properties

    CERN Document Server

    Smallwood, Ian

    2012-01-01

    The properties of 72 of the most commonly used solvents are given, tabulated in the most convenient way, making this book a joy for industrial chemists to use as a desk reference. The properties covered are those which answer the basic questions of: Will it do the job? Will it harm the user? Will it pollute the air? Is it easy to handle? Will it pollute the water? Can it be recovered or incinerated? These are all factors that need to be considered at the early stages of choosing a solvent for a new product or process.A collection of the physical properties of most commonly used solvents, their

  14. Caustic-Side Solvent Extraction Solvent-Composition Recommendation

    Energy Technology Data Exchange (ETDEWEB)

    Klatt, L.N.

    2002-05-09

    The U.S. Department of Energy has selected caustic-side solvent extraction as the preferred cesium removal technology for the treatment of high-level waste stored at the Savannah River Site. Data for the solubility of the extractant, calix[4]arene-bis(tert-octyl benzo-crown-6), acquired and reported for the Salt Processing Program down-select decision, showed the original solvent composition to be supersaturated with respect to the extractant. Although solvent samples have been observed for approximately 1 year without any solids formation, work was completed to define a new solvent composition that was thermodynamically stable with respect to solids formation and to expand the operating temperature with respect to third-phase formation. Chemical and physical data as a function of solvent component concentrations were collected. The data included calix[4]arene-bis(tert-octyl benzo-crown-6) solubility; cesium distribution ratio under extraction, scrub, and strip conditions; flow sheet robustness; temperature range of third-phase formation; dispersion numbers for the solvent against waste simulant, scrub and strip acids, and sodium hydroxide wash solutions; solvent density; viscosity; and surface and interfacial tension. These data were mapped against a set of predefined performance criteria. The composition of 0.007 M calix[4]arene-bis(tert-octyl benzo-crown-6), 0.75 M 1-(2,2,3,3-tetrafluoropropoxy)-3-(4-sec-butylphenoxy)-2-propanol, and 0.003 M tri-n-octylamine in the diluent Isopar{reg_sign} L provided the best match between the measured properties and the performance criteria. Therefore, it is recommended as the new baseline solvent composition.

  15. Allosteric changes in solvent accessibility observed in thrombin upon active site occupation.

    Science.gov (United States)

    Croy, Carrie Hughes; Koeppe, Julia R; Bergqvist, Simon; Komives, Elizabeth A

    2004-05-11

    The solvent accessibility of thrombin in its substrate-free and substrate-bound forms has been compared by amide hydrogen/deuterium (H/(2)H) exchange. The optimized inhibitor peptide dPhe-Pro-Arg chloromethyl ketone (PPACK) was used to simulate the substrate-bound form of thrombin. These studies were motivated by the lack of observed changes in the active site of thrombin in the crystal structure of the thrombin-thrombomodulin complex. This result appeared to contradict amide exchange studies on the thrombin-thrombomodulin complex that suggested subtle changes occur in the active site loops upon thrombomodulin binding. Our results show that two active site loops, residues 214-222 and residues 126-132, undergo decreases in solvent accessibility due to steric contacts with PPACK substrate. However, we also observe two regions outside the active site undergoing solvent protection upon substrate binding. The first region corresponds to anion binding exosite 1, and the second is a beta-strand-containing loop which runs through the core of the molecule and contains Trp141 which makes critical contacts with anion binding exosite 1. These results indicate two pathways of allosteric change that connect the active site to the distal anion binding exosite 1.

  16. Unconventional Face-On Texture and Exceptional In-Plane Order of a High Mobility n-Type Polymer

    KAUST Repository

    Rivnay, Jonathan

    2010-07-09

    Substantial in-plane crystallinity and dominant face-on stacking are observed in thin films of a high-mobility n-type rylene-thiophene copolymer. Spun films of the polymer, previously thought to have little or no order are found to exhibit an ordered microstructure at both interfaces, and in the bulk. The implications of this type of packing and crystalline morphology are discussed as they relate to thin-film transistors. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Impact of Quaternary climatic changes and interspecific competition on the demographic history of a highly mobile generalist carnivore, the coyote.

    Science.gov (United States)

    Koblmüller, Stephan; Wayne, Robert K; Leonard, Jennifer A

    2012-08-23

    Recurrent cycles of climatic change during the Quaternary period have dramatically affected the population genetic structure of many species. We reconstruct the recent demographic history of the coyote (Canis latrans) through the use of Bayesian techniques to examine the effects of Late Quaternary climatic perturbations on the genetic structure of a highly mobile generalist species. Our analysis reveals a lack of phylogeographic structure throughout the range but past population size changes correlated with climatic changes. We conclude that even generalist carnivorous species are very susceptible to environmental changes associated with climatic perturbations. This effect may be enhanced in coyotes by interspecific competition with larger carnivores.

  18. 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. Copyright © 2014 Elsevier B.V. All rights reserved.

  19. Practical Approaches to Green Solvents

    National Research Council Canada - National Science Library

    Joseph M. DeSimone

    2002-01-01

    Solvents are widely used in commercial manufacturing and service industries. Despite abundant precaution, they inevitably contaminate our air, land, and water because they are difficult to contain and recycle...

  20. ON-SITE SOLVENT RECOVERY

    Science.gov (United States)

    This study evaluated the product quality, waste reduction/pollution prevention, and economic aspects of three technologies for onsite solvent recovery: atmospheric batch distillation, vacuum heat-pump distillation, and low-emission vapor degreasing. The atmospheric and vacuum ...

  1. Hansen Cleaning Solvent Research Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Environmental regulation will force current baseline  precision cleaning solvent (AK-225) to be phased out starting 2015. We plan to develop  a new...

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

    Energy Technology Data Exchange (ETDEWEB)

    Bowman-James, Kristen

    2004-12-01

    This project have focuses on the basic chemical aspects of anion receptor design of functional pH independent systems, with the ultimate goal of targeting the selective binding of sulfate, as well as design of separations strategies for selective and efficient removal of targeted anions. Key findings include: (1) the first synthetic sulfate-selective anion-binding agents; (2) simple, structure-based methods for modifying the intrinsic anion selectivity of a given class of anion receptors; and (3) the first system capable of extracting sulfate anion from acidic, nitrate-containing aqueous media. Areas probed during the last funding period include: the design, synthesis, and physical and structural characterization of receptors and investigation of anion and dual ion pair extraction using lipophilic amide receptors for anion binding. A new collaboration has been added to the project in addition to the one with Dr. Bruce Moyer at Oak Ridge National Laboratory, with Professor Jonathan Sessler at the University of Texas at Austin.

  3. Unimolecular Solvolyses in Ionic Liquid: Alcohol Dual Solvent Systems

    Directory of Open Access Journals (Sweden)

    Elizabeth D. Kochly

    2016-01-01

    Full Text Available A study was undertaken of the solvolysis of pivaloyl triflate in a variety of ionic liquid:alcohol solvent mixtures. The solvolysis is a kΔ process (i.e., a process in which ionization occurs with rearrangement, and the resulting rearranged carbocation intermediate reacts with the alcohol cosolvent via two competing pathways: nucleophilic attack or elimination of a proton. Five different ionic liquids and three different alcohol cosolvents were investigated to give a total of fifteen dual solvent systems. 1H-NMR analysis was used to determine relative amounts of elimination and substitution products. It was found, not surprisingly, that increasing the bulkiness of alcohol cosolvent led to increased elimination product. The change in the amount of elimination product with increasing ionic liquid concentration, however, varied greatly between ionic liquids. These differences correlate strongly, though not completely, to the Kamlet–Taft solvatochromic parameters of the hydrogen bond donating and accepting ability of the solvent systems. An additional factor playing into these differences is the bulkiness of the ionic liquid anion.

  4. Higher plasma high-mobility group box 1 levels are associated with incident cardiovascular disease and all-cause mortality in type 1 diabetes

    DEFF Research Database (Denmark)

    Nin, J W M; Ferreira, I; Schalkwijk, C G

    2012-01-01

    This study aimed to investigate the associations of plasma levels of the pro-inflammatory cytokine high-mobility group box 1 (HMGB1) with incident cardiovascular disease (CVD) and all-cause mortality in patients with type 1 diabetes.......This study aimed to investigate the associations of plasma levels of the pro-inflammatory cytokine high-mobility group box 1 (HMGB1) with incident cardiovascular disease (CVD) and all-cause mortality in patients with type 1 diabetes....

  5. ATPD-2354 Revision 10 Verification Test, Disc Brake Version Only (16 NOV 06) Article Test of High Mobility Multipurpose Wheeled Vehicle (HMMWV-ECV)

    Science.gov (United States)

    2007-05-23

    070169 ATPD-2354 REVISION 10 VERIFICATION TEST, DISC BRAKE VERSION ONLY (16 NOV 06) ARTICLE TEST OF HIGH MOBILITY MULTIPURPOSE WHEELED...Verification Test, Disc Brake Verson Only (16 NOV 06) Article Test of High Mobility Multipurpose Wheeled Vehicle (HMMWV-ECV) 5a. CONTRACT NUMBER...different characteristics critical to the proper field service of the brake pads and rotor combination, an assortment of tests was conducted to evaluate

  6. Sodium-ion electrolytes based on ionic liquids: a role of cation-anion hydrogen bonding.

    Science.gov (United States)

    Chaban, Vitaly V; Andreeva, Nadezhda A

    2016-08-01

    Recent success of the sodium-ion batteries fosters an academic interest for their investigation. Room-temperature ionic liquids (RTILs) constitute universal solvents providing non-volatility and non-flammability to electrolytes. In the present work, we consider four families of RTILs as prospective solvents for NaBF4 and NaNO3 with an inorganic salt concentration of 25 and 50 mol%. We propose a methodology to rate RTILs according to their solvation capability using parameters of the computed radial distribution functions. Hydrogen bonds between the cations and the anions of RTILs were found to indirectly favor sodium solvation, irrespective of the particular RTIL and its concentration. The best performance was recorded in the case of cholinium nitrate. The reported observations and correlations of ionic structures and properties offer important assistance to an emerging field of sodium-ion batteries. Graphical Abstract Sodium-ion electrolytes.

  7. Synthesis and Characterization of Anionic Polyester-Polyurethane Dispersion as Environmentally-Friendly Waterbased Resins

    Directory of Open Access Journals (Sweden)

    Najaf i F. Manouchehri F., and Shaabanz

    2012-01-01

    Full Text Available Aqueous polyurethane dispersions (PUDs have recently emerged as important alternatives to their solvent-based counterparts for various applications due to increasing health and environmental awareness (green chemistry. Anionic polyester-polyurethane dispersions were synthesized by three steps. In the first step, macromonomer diisocyanate having carboxylic acid was prepared by isophorone diisocyanate (IPDI, dimethylol propionic acid (DMPA in percent of acetone as solvent and dibutyldtin dilaurate (DBTDL as catalyst. Then, carboxylic polyurethane was prepared by reaction macromonomer diisocyanate having carboxylic acid with linear aliphatic polyester (Mw=2000, trifunctional polyester (Mw=2800 and butanediol (BDO as chain extender. The next step involved neutralization and dispersion in water, where acidic polyurethane was neutralized by the addition of triethylamine (TEA.  Factors influencing the synthesis of polyurethane dispersion mainly involve reaction temperature, reaction time, the concentration of catalyst, DMPA content and BDO content, were studied. The polymers have been characterized with DSC and FTIR.

  8. High mobility La-doped BaSnO3 on non-perovskite MgO substrate

    Science.gov (United States)

    Kim, Youjung; Shin, Juyeon; Kim, Young Mo; Char, Kookrin

    (Ba,La)SnO3 is a transparent perovskite oxide with high electron mobility and excellent oxygen stability. Field effect device with (Ba,La)SnO3 channel was reported to show good output characteristics on STO substrate. Here, we fabricated (Ba,La)SnO3\\ films and field effect devices with (Ba,La)SnO3 channel on non-perovskite MgO substrates, which are available in large size wafers. X-ray diffraction and transmission electron microscope (TEM) images of (Ba,La)SnO3\\ films on MgO substrates show that the films are epitaxial with many threading dislocations. (Ba,La)SnO3 exhibits the high mobility with 97.2 cm2/Vs at 2 % La doping on top of 150 nm thick BaSnO3 buffer layer. Excellent carrier modulation was observed in field effect devices. FET performances on MgO substrates are slightly better than those on SrTiO3 substrates in spite of the higher dislocation density on MgO than on SrTiO3 substrates. These high mobility BaSnO3 thin films and transistors on MgO substrates will accelerate development for applications in high temperature and high power electronics. Samsung Science and Technology Foundation.

  9. Vapor-Liquid Equilibria of Imidazolium Ionic Liquids with Cyano Containing Anions with Water and Ethanol.

    Science.gov (United States)

    Khan, Imran; Batista, Marta L S; Carvalho, Pedro J; Santos, Luís M N B F; Gomes, José R B; Coutinho, João A P

    2015-08-13

    Isobaric vapor-liquid equilibria of 1-butyl-3-methylimidazolium thiocyanate ([C4C1im][SCN]), 1-butyl-3-methylimidazolium dicyanamide ([C4C1im][N(CN)2]), 1-butyl-3-methylimidazolium tricyanomethanide ([C4C1im][C(CN)3]), and 1-ethyl-3-methylimidazolium tetracyanoborate ([C2C1im][B(CN)4]), with water and ethanol were measured over the whole concentration range at 0.1, 0.07, and 0.05 MPa. Activity coefficients were estimated from the boiling temperatures of the binary systems, and the data were used to evaluate the ability of COSMO-RS for describing these molecular systems. Aiming at further understanding the molecular interactions on these systems, molecular dynamics (MD) simulations were performed. On the basis of the interpretation of the radial and spatial distribution functions along with coordination numbers obtained through MD simulations, the effect of the increase of CN-groups in the IL anion in its capability to establish hydrogen bonds with water and ethanol was evaluated. The results obtained suggest that, for both water and ethanol systems, the anion [N(CN)2](-) presents the higher ability to establish favorable interactions due to its charge, and that the ability of the anions to interact with the solvent, decreases with further increasing of the number of cyano groups in the anion. The ordering of the partial charges in the nitrogen atoms from the CN-groups in the anions agrees with the ordering obtained for VLE and activity coefficient data.

  10. Solvent engineering for high-quality perovskite solar cell with an efficiency approaching 20%

    Science.gov (United States)

    Wu, Tongyue; Wu, Jihuai; Tu, Yongguang; He, Xin; Lan, Zhang; Huang, Miaoliang; Lin, Jianming

    2017-10-01

    The perovskite layer is the most crucial factor for the high performance perovskite solar cells. Based on solvent engineering, we develop a ternary-mixed-solvent method for the growth of high-quality [Cs0.05(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3] cation-anion-mixed perovskite films by introducing N-methyl-2-pyrrolidone (NMP) into the precursor mixed solution. By controlling rapid nucleation and retarding crystal growth via intermediate phase PbI2-NMP (Lewis acid-base adduct), a dense, large grain, pinhole-free and long charge carrier lifetime perovskite film is obtained. By optimizing the precursor solvent composition, the perovskite solar cell achieves an impressive power conversion efficiency of 19.61% under one-sun illumination. The research presented here provides a facile, low-cost and highly efficient way for the preparation of perovskite solar cells.

  11. Solvents interactions with thermochromic print

    Directory of Open Access Journals (Sweden)

    Mirela Rožić

    2017-12-01

    Full Text Available In this study, the interactions between different solvents (benzene, acetone, cyclohexanone, various alcohols and water and thermochromic printing ink were investigated. Thermochromic printing ink was printed on metal surface. Components of thermochromic printing inks are polymeric microcapsules and classic yellow offset printing ink. Below its activation temperature, dye and developer within the microcapsules form a blue coloured complex. Therefore, thermochromic print is green. By heating above the activation temperature, blue colour of the complex turns into the leuco dye colourless state and the green colour of the prints turns into the yellow colour of the classic offset pigment. The results of the interaction with various solvents show that the thermochromic print is stable in all tested solvents except in ethanol, acetone and cyclohexanone. In ethanol, the green colour of the print becomes yellow. SEM analysis shows that microcapsules are dissolved. In acetone and cyclohexanone, the green colour of the print turns into blue, and the microcapsules become significantly more visible. Thus, the yellow pigment interacts with examined ketones. Based on the obtained interactions it can be concluded that the microcapsules have more polar nature than the classical pigment particles. Solvent-thermocromic print interactions were analysed using Hansen solubility parameters that rank the solvents based on their estimated interaction capabilities.

  12. Sustainable and Low Viscous 1-Allyl-3-methylimidazolium Acetate + PEG Solvent for Cellulose Processing

    Directory of Open Access Journals (Sweden)

    Airong Xu

    2017-02-01

    Full Text Available Developing sustainable, low viscous and efficient solvents are always advantageous to the processing/fabricating of cellulose materials in practical applications. To this end, in this work novel solvents were developed; ([Amim][CH3COO]/PEG by dissolving polyethylene glycol 200 (PEG-200 in 1-allyl-3-methylimidazolium acetate ([Amim][CH3COO]. The solubilities of cellulose in [Amim][CH3COO]/PEG solvents were determined as a function of temperature, and the possible dissolution mechanism of cellulose in [Amim][CH3COO]/PEG solvent was investigated. The novel solvent exhibits outstanding advantages for good dissolution capacity of cellulose, such as low viscosity, negligible vapor pressure, and recycling capability. The [CH3COO]− anion and the [Amim]+ cation of [Amim][CH3COO] in [Amim][CH3COO]/PEG-10 are the driving force for cellulose dissolution verified by the 13C NMR spectra. In addition, the regenerated cellulose films from [Amim][CH3COO]/PEG solvent were characterized by scanning electron microscopy (SEM, X-ray diffraction (XRD, attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR, and thermogravimetric analysis (TGA to estimate their morphologies and structures.

  13. 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

    Historically, the anion transport through the human red cell membrane has been perceived to be mediated by Band 3, in the two-component concept with the large electroneutral anion exchange accompanied by the conductance proper, which dominated the total membrane conductance. The status of anion...... to the red cell than the ground leak mediated by Band 3....... 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...

  14. Computer simulation of methanol exchange dynamics around cations and anions

    Energy Technology Data Exchange (ETDEWEB)

    Roy, Santanu; Dang, Liem X.

    2016-03-03

    In this paper, we present the first computer simulation of methanol exchange dynamics between the first and second solvation shells around different cations and anions. After water, methanol is the most frequently used solvent for ions. Methanol has different structural and dynamical properties than water, so its ion solvation process is different. To this end, we performed molecular dynamics simulations using polarizable potential models to describe methanol-methanol and ion-methanol interactions. In particular, we computed methanol exchange rates by employing the transition state theory, the Impey-Madden-McDonald method, the reactive flux approach, and the Grote-Hynes theory. We observed that methanol exchange occurs at a nanosecond time scale for Na+ and at a picosecond time scale for other ions. We also observed a trend in which, for like charges, the exchange rate is slower for smaller ions because they are more strongly bound to methanol. This work was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. The calculations were carried out using computer resources provided by the Office of Basic Energy Sciences.

  15. Multiple sclerosis and organic solvents

    DEFF Research Database (Denmark)

    Mortensen, J T; Brønnum-Hansen, Henrik; Rasmussen, K

    1998-01-01

    We investigated a possible causal relation between exposure to organic solvents in Danish workers (housepainters, typographers/printers, carpenters/cabinetmakers) and onset of multiple sclerosis. Data on men included in the Danish Multiple Sclerosis Register (3,241 men) were linked with data from......, and butchers. Over a follow-up period of 20 years, we observed no increase in the incidence of multiple sclerosis among men presumed to be exposed to organic solvents. It was not possible to obtain data on potential confounders, and the study design has some potential for selection bias. Nevertheless......, the study does not support existing hypotheses regarding an association between occupational exposure to organic solvents and multiple sclerosis....

  16. 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-

  17. Mechanisms of renal anionic drug transport.

    NARCIS (Netherlands)

    El-Sheikh, A.A.K.; Masereeuw, R.; Russel, F.G.M.

    2008-01-01

    By utilizing filtration, active secretion and reabsorption processes, the kidney can conserve essential nutrients, and eliminate drugs and potentially toxic compounds. Active uptake of organic anions and cations across the basolateral membrane, and their extrusion into the urine across the brush

  18. 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

  19. Anion exchange membrane design for reverse electrodialysis

    NARCIS (Netherlands)

    Güler, E.

    2014-01-01

    Reverse electrodialysis (RED) is a clean, sustainable technology for the generation of energy from the mixing of solutions with different salinity. The ion exchange membranes are key elements in RED. Especially the study of anion exchange membranes is crucial since limited research has been done

  20. Anion-Conducting Polymer, Composition, and Membrane

    Science.gov (United States)

    Pivovar, Bryan S.; Thorn, David L.

    2008-10-21

    Anion-conducing polymers and membranes with enhanced stability to aqueous alkali include a polymer backbone with attached sulfonium, phosphazenium, phosphazene, and guanidinium residues. Compositions also with enhanced stability to aqueous alkali include a support embedded with sulfonium, phosphazenium, and guanidinium salts.

  1. Optical conductivity and optical effective mass in a high-mobility organic semiconductor: Implications for the nature of charge transport

    KAUST Repository

    Li, Yuan

    2014-12-03

    We present a multiscale modeling of the infrared optical properties of the rubrene crystal. The results are in very good agreement with the experimental data that point to nonmonotonic features in the optical conductivity spectrum and small optical effective masses. We find that, in the static-disorder approximation, the nonlocal electron-phonon interactions stemming from low-frequency lattice vibrations can decrease the optical effective masses and lead to lighter quasiparticles. On the other hand, the charge-transport and infrared optical properties of the rubrene crystal at room temperature are demonstrated to be governed by localized carriers driven by inherent thermal disorders. Our findings underline that the presence of apparently light carriers in high-mobility organic semiconductors does not necessarily imply bandlike transport.

  2. Academic Achievement Trajectories of Homeless and Highly Mobile Students: Resilience in the Context of Chronic and Acute Risk

    Science.gov (United States)

    Cutuli, J. J.; Desjardins, Christopher David; Herbers, Janette E.; Long, Jeffrey D.; Heistad, David; Chan, Chi-Keung; Hinz, Elizabeth; Masten, Ann S.

    2012-01-01

    Analyses examined academic achievement data across 3rd through 8th grades (N = 26,474), comparing students identified as homeless or highly mobile (HHM) to other students in the federal free meal program (FM), reduced-price meals (RM), or neither (General). Achievement was lower as a function of rising risk status (General > RM > FM > HHM). Achievement gaps appeared stable or widened between HHM students and lower-risk groups. Math and reading achievement were lower and growth in math was slower in years of HHM identification, suggesting acute consequences of residential instability. Nonetheless, 45% of HHM students scored within or above the average range, suggesting academic resilience. Results underscore the need for research on risk and resilience processes among HHM students to address achievement disparities. PMID:23110492

  3. Sequence-specific high mobility group box factors recognize 10-12-base pair minor groove motifs

    DEFF Research Database (Denmark)

    van Beest, M; Dooijes, D; van De Wetering, M

    2000-01-01

    , 12, and 10 base pairs, respectively. Footprinting with a deletion mutant of Ste11 reveals a novel interaction between the 3' base pairs of the extended DNA motif and amino acids C-terminal to the HMG domain. The sequence-specific interaction of Ste11 with these 3' base pairs contributes significantly......Sequence-specific high mobility group (HMG) box factors bind and bend DNA via interactions in the minor groove. Three-dimensional NMR analyses have provided the structural basis for this interaction. The cognate HMG domain DNA motif is generally believed to span 6-8 bases. However, alignment...... of promoter elements controlled by the yeast genes ste11 and Rox1 has indicated strict conservation of a larger DNA motif. By site selection, we identify a highly specific 12-base pair motif for Ste11, AGAACAAAGAAA. Similarly, we show that Tcf1, MatMc, and Sox4 bind unique, highly specific DNA motifs of 12...

  4. Electron heating due to microwave photoexcitation in the high mobility GaAs/AlGaAs two dimensional electron system

    Energy Technology Data Exchange (ETDEWEB)

    Ramanayaka, A. N.; Mani, R. G. [Department of Physics and Astronomy, Georgia State University, Atlanta, Georgia 30303 (United States); Wegscheider, W. [Laboratorium für Festkörperphysik, ETH Zürich, CH-8093 Zürich (Switzerland)

    2013-12-04

    We extract the electron temperature in the microwave photo-excited high mobility GaAs/AlGaAs two dimensional electron system (2DES) by studying the influence of microwave radiation on the amplitude of Shubnikov-de Haas oscillations (SdHOs) in a regime where the cyclotron frequency, ω{sub c}, and the microwave angular frequency, ω, satisfy 2ω ≤ ω{sub c} ≤ 3.5ω The results indicate that increasing the incident microwave power has a weak effect on the amplitude of the SdHOs and therefore the electron temperature, in comparison to the influence of modest temperature changes on the dark-specimen SdH effect. The results indicate negligible electron heating under modest microwave photo-excitation, in good agreement with theoretical predictions.

  5. Enabling high-mobility, ambipolar charge-transport in a DPP-benzotriazole copolymer by side-chain engineering

    DEFF Research Database (Denmark)

    Gruber, Mathias; Jung, Seok-Heon; Schott, Sam

    2015-01-01

    side-chain on the DPP-unit leads to an increase in thin-film order and charge-carrier mobility if a sufficiently solubilizing, branched, side chain is attached to the BTZ. We compare two different synthetic routes, direct arylation and Suzuki-polycondensation, by a direct comparison of polymers...... exceptionally high and near balanced average electron and hole mobilities >2 cm2 V-1 s-1 which are among the highest, robustly extracted mobility values reported for DPP copolymers in a top-gate configuration to date. Our results demonstrate clearly that linear side chain substitution of the DPP unit together...... with co-monomers that allow for the use of sufficiently long or branched solubilizing side chains can be an attractive design motif for solution processable, high mobility DPP copolymers....

  6. The Role of High-Mobility Group Box-1 and Its Crosstalk with Microbiome in Rheumatoid Arthritis

    Science.gov (United States)

    Flex, Andrea; Alivernini, Stefano; Tolusso, Barbara; Gremese, Elisa

    2017-01-01

    Rheumatoid arthritis (RA) is a chronic, definitely disabling, and potentially severe autoimmune disease. Although an increasing number of patients are affected, a key treatment for all patients has not been discovered. High-mobility group box-1 (HMGB1) is a nuclear protein passively and actively released by almost all cell types after several stimuli. HMGB1 is involved in RA pathogenesis, but a convincing explanation about its role and possible modulation in RA is still lacking. Microbiome and its homeostasis are altered in patients with RA, and the microbiota restoration has been proposed to patients with RA. The purpose of the present review is to analyze the available evidences regarding HMGB1 and microbiome roles in RA and the possible implications of the crosstalk between the nuclear protein and microbiome in understanding and possibly treating patients affected by this harmful condition. PMID:29200665

  7. Levels of high-mobility group box-1 in gingival crevicular fluid in nonsmokers and smokers with chronic periodontitis

    Directory of Open Access Journals (Sweden)

    Yi-Chun Lin

    2017-12-01

    Full Text Available Background/Purpose: High-mobility group box-1 (HMGB1, a proinflammatory cytokine, plays a role in inflammatory disorders. Smoking is a well-established risk factor for periodontal disease. The aim of this study was to compare the levels of HMGB1 in the gingival crevicular fluid from periodontally healthy nonsmokers, chronic periodontitis nonsmokers, and chronic periodontitis smokers. Furthermore, the relationship between levels of HMGB1 and periodontal parameters was examined. Methods: Periodontal parameters of 17 nonsmokers with chronic periodontitis, nine smokers with chronic periodontitis, and nine periodontally healthy nonsmokers were examined. Gingival crevicular fluid samples were collected, and the levels of HMGB1 were analyzed using the enzyme-linked immunosorbent assay. Results: The median level of HMGB1 was statistically significantly higher in chronic periodontitis nonsmokers (37.5 ng/mL than in chronic periodontitis smokers (9.5 ng/mL and periodontally healthy nonsmokers (3.7 ng/mL. There was no significant difference in the levels of HMGB1 between chronic periodontitis smokers and periodontally healthy nonsmokers. Levels of HMGB1 were positively correlated with plaque index, gingival index, probing depth, and clinical attachment level of nonsmokers. However, no significant correlations were found between levels of HMGB1 and all periodontal parameters examined in chronic periodontitis smokers. Conclusion: Chronic periodontitis nonsmokers had elevated levels of HMGB1 in gingival crevicular fluid. Moreover, the levels of HMGB1 were correlated with severity of periodontitis. Chronic periodontitis smokers exhibited lower levels of HMGB1 than chronic periodontitis nonsmokers. Further research is needed for understanding the role of HMGB1 in smoking and pathogenesis of periodontitis. Keywords: gingival crevicular fluid, high-mobility group box-1, periodontitis, smoking

  8. Cyanide anion binding by a triarylborane at the outer rim of a cyclometalated ruthenium(II) cationic complex.

    Science.gov (United States)

    Wade, Casey R; Gabbaï, François P

    2010-01-18

    As part of our ongoing interest in the design of boron-based cyanide anion receptors, we have synthesized a triaryl borane decorated by a cationic Ru(II) complex and have investigated its anion binding properties. This new borane, [(2,2'-bpy)Ru(kappa-C,N-2-(dimesitylborylphenyl)pyridinato)]OTf ([2]OTf), binds both fluoride and cyanide anions in organic solvents to afford 2-F and 2-CN whose crystal structures have been determined. UV-vis titrations in 9/1 CHCl(3)/DMF (vol.) afforded K((F(-))) = 1.1(+/-0.1) x 10(4) M(-1) and K((CN(-))) = 3.0(+/-1.0) x 10(6) M(-1) indicating that [2](+) has a higher affinity for cyanide than for fluoride in this solvent mixture. These elevated binding constants show that the cationic Ru(II) complex increases the anion affinity of these complexes via Coulombic and inductive effects. The UV-vis spectral changes which accompany either fluoride or cyanide binding to the boron center are similar and include a 30 nm bathochromic shift of the metal-to-ligand charge transfer band. This shift is attributed to an increase in the donor ability of the boron-substituted phenylpyridine ligand upon anion binding to the boron center. Accordingly, cyclic voltammetry revealed that the Ru(II/III) redox couple of [2]OTf (E(1/2) = +0.051 V vs Fc/Fc(+)) undergoes a cathodic shift upon F(-) (DeltaE(1/2) = -0.242 V vs Fc/Fc(+)) or CN(-) (DeltaE(1/2) = -0.198 V vs Fc/Fc(+)) binding.

  9. Synthesis and anion-exchange reactions of a new anionic clay, α-magnesium hydroxide.

    Science.gov (United States)

    Nethravathi, C; Rajamathi, Jacqueline T; George, Preeta; Rajamathi, Michael

    2011-02-15

    A new anionic clay, α-magnesium hydroxide, was synthesized by hydrolysis of magnesium acetate in propylene glycol. The structure of this α-hydroxide is similar to that of hydrotalcites. It consists of positively charged magnesium hydroxide layers arising out of partial protonation of the hydroxyl groups of the [Mg(OH)(2)] layers and loosely held anions in the interlayer region. As expected it ages readily in water to give β-magnesium hydroxide, brucite. While anion-exchange reactions of α-magnesium hydroxide could not be carried out in aqueous medium a number of anion-exchange reactions could be carried out successfully in ethanol medium. Copyright © 2010 Elsevier Inc. All rights reserved.

  10. Benzodipyrrole derivates as new ionophores for anion-selective electrodes: improving potentiometric selectivity towards divalent anions.

    Science.gov (United States)

    Cuartero, M; Ortuño, J A; García, M S; Sánchez, G; Más-Montoya, M; Curiel, D

    2011-09-30

    Two open substituted benzodipyrroles were tested as hydrogen-bond-forming anion ionophores for the development of anion-selective electrodes. These compounds were incorporated in plasticized polymeric membranes with different plasticizers, using different membrane compositions to explore their response towards several anions. The electrodes constructed with membranes containing 2-nitrophenyl octyl ether and a 0.5 molar ratio ionic additive/ionophore showed pronounced anti-Hofmeister behaviour, providing a significantly enhanced response towards the divalent anions sulfate, sulfite, thiosulfate and oxalate. The selected electrodes were also evaluated in terms of detection limits and selectivity. (1)H NMR experiments were carried out in an attempt to explain some aspects of the behaviour observed. Copyright © 2011 Elsevier B.V. All rights reserved.

  11. Femtosecond photoelectron spectroscopy: a new tool for the study of anion dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Greenblatt, Benjamin J. [Univ. of California, Berkeley, CA (United States)

    1999-02-01

    A new experimental technique for the time-resolved study of anion reactions is presented. Using femtosecond laser pulses, which provide extremely fast (~100 fs) time resolution, in conjunction with photoelectron spectroscopy, which reveals differences between anion and neutral potential energy surfaces, a complex anion reaction can be followed from its inception through the formation of asymptotic products. Experimental data can be modeled quantitatively using established theoretical approaches, allowing for the refinement of potential energy surfaces as well as dynamical models. After a brief overview, a detailed account of the construction of the experimental apparatus is presented. Documentation of the data acquisition program is contained in the Appendix. The first experimental demonstration of the technique is then presented for I2- photodissociation, modeled using a simulation program which is also detailed in the Appendix. The investigation of I2- photodissociation in several size-selected I2-(Ar)n (n = 6-20) and I2-(CO2)n (n = 4-16) clusters forms the heart of the dissertation. In a series of chapters, the numerous effects of solvation on this fundamental bond-breaking reaction are explored, the most notable of which is the recombination of I2- on the ground $\\tilde{X}$(2Σu+) state in sufficiently large clusters. Recombination and trapping of I2- on the excited $\\tilde{A}$(2π3/2,g) state is also observed in both types of clusters. The studies have revealed electronic state transitions, the first step in recombination, on a ~500 fs to ~10 ps timescale. Accompanying the changes in electronic state is solvent reorganization, which occurs on a similar timescale. Over longer periods (~1 ps to >200 ps), energy is transferred from vibrationally

  12. Advances in anion supramolecular chemistry: from recognition to chemical applications.

    Science.gov (United States)

    Evans, Nicholas H; Beer, Paul D

    2014-10-27

    Since the start of this millennium, remarkable progress in the binding and sensing of anions has been taking place, driven in part by discoveries in the use of hydrogen bonding, as well as the previously under-exploited anion-π interactions and halogen bonding. However, anion supramolecular chemistry has developed substantially beyond anion recognition, and now encompasses a diverse range of disciplines. Dramatic advance has been made in the anion-templated synthesis of macrocycles and interlocked molecular architectures, while the study of transmembrane anion transporters has flourished from almost nothing into a rapidly maturing field of research. The supramolecular chemistry of anions has also found real practical use in a variety of applications such as catalysis, ion extraction, and the use of anions as stimuli for responsive chemical systems. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Chlorinated solvents in a petrochemical wastewater treatment plant: an assessment of their removal using self-organising maps.

    Science.gov (United States)

    Tobiszewski, Marek; Tsakovski, Stefan; Simeonov, Vasil; Namieśnik, Jacek

    2012-05-01

    The self-organising map approach was used to assess the efficiency of chlorinated solvent removal from petrochemical wastewater in a refinery wastewater treatment plant. Chlorinated solvents and inorganic anions (11 variables) were determined in 72 wastewater samples, collected from three different purification streams. The classification of variables identified technical solvents, brine from oil desalting and runoff sulphates as pollution sources in the refinery, affecting the quality of wastewater treatment plant influent. The classification of samples revealed the formation of five clusters: the first three clusters contained samples collected from the drainage water, process water and oiled rainwater treatment streams. The fourth cluster consisted mainly of samples collected after biological treatment, and the fifth one of samples collected after an unusual event. SOM analysis showed that the biological treatment step significantly reduced concentrations of chlorinated solvents in wastewater. Copyright © 2012 Elsevier Ltd. All rights reserved.

  14. Photosensitized electron transfer from sterically hindered amines to the benzophenone triplet and its reversion in solvents of different polarity

    Science.gov (United States)

    Kluge, T.; Brede, O.

    1998-06-01

    The reductive quenching of the benzophenone triplet by 2,2,6,6-tetramethyl- and 1,2,2,6,6-pentamethyl-piperidine was studied by laser flash photolysis. The rate constants for the quenching process were obtained in solvents of different polarity, acetonitrile, methanol, acetone, n-butanol, t-butanol, butyl chloride, chloroform, 1,4-dioxane, cyclohexane and benzene. The contact ion pair primarily formed, decays by proton transfer under the formation of the benzophenone ketyl radical, back electron transfer and charge separation. In our experiments no indication for the free solvated anion radical was found. The ketyl radical yields vary with solvent polarity, showing a minimum for the solvent butyl chloride. We explain this behaviour in terms of the solvent dependence of the back electron transfer process. Rate constants were determined for all reactions studied.

  15. Hydrogen Production from a Methanol-Water Solution Catalyzed by an Anionic Iridium Complex Bearing a Functional Bipyridonate Ligand under Weakly Basic Conditions.

    Science.gov (United States)

    Fujita, Ken-ichi; Kawahara, Ryoko; Aikawa, Takuya; Yamaguchi, Ryohei

    2015-07-27

    An efficient catalytic system for the production of hydrogen from a methanol-water solution has been developed using a new anionic iridium complex bearing a functional bipyridonate ligand as a catalyst. This system can be operated under mild conditions [weakly basic solution (0.046 mol L(-1) NaOH) below 100 °C] without the use of an additional organic solvent. Long-term continuous hydrogen production from a methanol-water solution catalyzed by the anionic iridium complex was also achieved. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Electrochemical investigations of antioxidant interactions with radical anion and dianion of 1,3-dinitrobenzene

    Energy Technology Data Exchange (ETDEWEB)

    Arshad, Nasima [Department of Chemistry, Allama Iqbal Open University, Islamabad (Pakistan); Janjua, Naveed Kausar [Department of Chemistry, Quaid-i-Azam University, Islamabad (Pakistan)], E-mail: nkausarjanjua@yahoo.com; Ahmed, Safeer [Department of Chemistry, Quaid-i-Azam University, Islamabad (Pakistan); Khan, Athar Yaseen [Department of Chemistry, Allama Iqbal Open University, Islamabad (Pakistan); Skibsted, Leif H. [Food Chemistry, Department of Food Science, University of Copenhagen (Denmark)

    2009-11-01

    Interactions of five antioxidants (AO), quercetin (Q), morin (M), rutin (R), ascorbic acid (AA) and {beta}-carotene ({beta}-C) with anion radical and dianion of 1,3-dinitrobenzene (1,3-DNB) in two aprotic solvents - dimethyl formamide (DMF) and dimethyl sulfoxide (DMSO) - have been studied by cyclic voltammetry using glassy carbon electrode. Electrochemical parameters - peak potential (E{sub p}), half-wave potential (E{sub 1/2}), and peak current (i{sub p}) - for the reduction of 1,3-DNB before and after the addition of various concentrations of antioxidants, were evaluated. A gradual decrease in the oxidation peak current and finally irreversibility in 1,3-DNB radical anion and dianion systems upon the addition of antioxidant, reveals their interactions. The homogeneous bi-molecular rate constant (k{sub 2}) was determined from electrochemical data. In comparison to all other antioxidants used, enhanced homogeneous second order rate constant for the interaction of morin with 1,3-DNB anion radical and dianion, was observed. This aspect is attributable to protonation initiated by hydrogen bonding and greater acidic nature of morin.

  17. 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.

  18. Quantum Mechanics of In Situ Synthesis of Metal Nanoparticles within Anionic Microgels

    Directory of Open Access Journals (Sweden)

    Mirza Wasif Baig

    2013-01-01

    Full Text Available We discuss the quantum mechanics of many-body systems, that is, hybrid microgel consisting of negatively charged anionic microgels possessing thick sheath of water molecules solvating protruding anionic moieties and nanoparticle captivated within the microgel. Thermodynamic feasibility of synthesis of particular nanoparticle within the microgel is dependent upon the magnitude of interaction between nanoparticle, water molecules, and microgel relative to sum of magnitude of self-interaction between counterions and interaction between counterions and microgel. Nanoparticles synthesized with in the microgels have thick electronic cloud that oscillates under the influence of net interaction potential of charged anionic moieties and solvent water molecules which constitutes the chemical environment of hybrid microgel. Hamiltonian describing energy of oscillating electronic cloud of wrapped around nanoparticle is mathematically derived to be equal to product of integral electron density and product of its position vector overall space and net force acting on the oscillating electronic cloud of nanoparticle is mathematically defined as; ℱ∫ρn{n}n^ dn.

  19. Computer-aided tool for solvent selection in pharmaceutical processes: Solvent swap

    DEFF Research Database (Denmark)

    Papadakis, Emmanouil; K. Tula, Anjan; Gernaey, Krist V.

    In the pharmaceutical processes, solvents have a multipurpose role since different solvents can be used in different stages (such as chemical reactions, separations and purification) in the multistage active pharmaceutical ingredients (APIs) production process. The solvent swap and selection task...

  20. Organic Solvent Effects in Biomass Conversion Reactions.

    Science.gov (United States)

    Shuai, Li; Luterbacher, Jeremy

    2016-01-01

    Transforming lignocellulosic biomass into fuels and chemicals has been intensely studied in recent years. A large amount of work has been dedicated to finding suitable solvent systems, which can improve the transformation of biomass into value-added chemicals. These efforts have been undertaken based on numerous research results that have shown that organic solvents can improve both conversion and selectivity of biomass to platform molecules. We present an overview of these organic solvent effects, which are harnessed in biomass conversion processes, including conversion of biomass to sugars, conversion of sugars to furanic compounds, and production of lignin monomers. A special emphasis is placed on comparing the solvent effects on conversion and product selectivity in water with those in organic solvents while discussing the origins of the differences that arise. We have categorized results as benefiting from two major types of effects: solvent effects on solubility of biomass components including cellulose and lignin and solvent effects on chemical thermodynamics including those affecting reactants, intermediates, products, and/or catalysts. Finally, the challenges of using organic solvents in industrial processes are discussed from the perspective of solvent cost, solvent stability, and solvent safety. We suggest that a holistic view of solvent effects, the mechanistic elucidation of these effects, and the careful consideration of the challenges associated with solvent use could assist researchers in choosing and designing improved solvent systems for targeted biomass conversion processes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Several hemicyanine dyes as fluorescence chemosensors for cyanide anions

    Science.gov (United States)

    Liang, Muhan; Wang, Kangnan; Guan, Ruifang; Liu, Zhiqiang; Cao, Duxia; Wu, Qianqian; Shan, Yanyan; Xu, Yongxiao

    2016-05-01

    Four hemicyanine dyes as chemosensors for cyanide anions were synthesized easily. Their photophysical properties and recognition properties for cyanide anions were investigated. The results indicate that all the dyes can recognize cyanide anions with obvious color, absorption and fluorescence change. The recognition mechanism analysis basing on in situ 1H NMR and Job plot data indicates that to the compounds with hydroxyl group, the recognition mechanism is intramolecular hydrogen bonding interaction. However, to the compounds without hydroxyl group, cyanide anion is bonded to carbon-carbon double bond in conjugated bridge and induces N+ CH3 to neutral NCH3. Fluorescence of the compounds is almost quenched upon the addition of cyanide anions.

  2. 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

  3. Empirical correlation methods for temporary anions.

    Science.gov (United States)

    Sommerfeld, Thomas; Weber, Rebecca J

    2011-06-23

    A temporary anion is a short-lived radical anion that decays through electron autodetachment into a neutral molecule and a free electron. The energies of these metastable species are often predicted using empirical correlation methods because ab initio predictions are computationally very expensive. Empirical correlation methods can be justified in the framework of Weisskopf-Fano-Feshbach theory but tend to work well only within closely related families of molecules or within a restricted energy range. The reason for this behavior can be understood using an alternative theoretical justification in the framework of the Hazi-Taylor stabilization method, which suggests that the empirical parameters do not so much correct for the coupling of the computed state to the continuum but for electron correlation effects and that therefore empirical correlation methods can be improved by using more accurate electronic structure methods to compute the energy of the confined electron. This idea is tested by choosing a heterogeneous reference set of temporary states and comparing empirical correlation schemes based on Hartree-Fock orbital energies, Kohn-Sham orbital energies, and attachment energies computed with the equation-of-motion coupled-cluster method. The results show that using more reliable energies for the confined electron indeed enhances the predictive power of empirical correlation schemes and that useful correlations can be established beyond closely related families of molecules. Certain types of σ* states are still problematic, and the reasons for this behavior are analyzed. On the other hand, preliminary results suggest that the new scheme can even be useful for predicting energies of bound anions at a fraction of the computational cost of reliable ab initio calculations. It is then used to make predictions for bound and temporary states of the furantrione and croconic acid radical anions.

  4. Can the tricyanomethanide anion improve CO2 absorption by acetate-based ionic liquids?

    Science.gov (United States)

    Lepre, L F; Szala-Bilnik, J; Pison, L; Traïkia, M; Pádua, A A H; Ando, R A; Costa Gomes, M F

    2017-05-17

    Carbon dioxide absorption by mixtures of two ionic liquids with a common cation-1-butyl-3-methylimidazolium acetate, [C4C1Im][OAc], and 1-butyl-3-methylimidazolium tricyanomethanide, [C4C1Im][C(CN)3]-was determined experimentally at pressures below atmospheric pressure as a function of temperature between 303 K and 343 K, and at 303 K as a function of pressure up to 10 bar. It is observed that the absorption of carbon dioxide decreases with increasing tricyanomethanide anion concentration and with increasing temperature, showing a maximum of 0.4 mole fraction of carbon dioxide in pure [C4C1Im][OAc] at 303 K. At this temperature, the CO2 absorption in the mixtures [C4C1Im][OAc](1-x)[C(CN)3]x is approximately the mole-fraction average of that in the pure ionic liquids. By applying an appropriate thermodynamic treatment, after identification of the species in solution, it was possible to calculate both the equilibrium constant, Keq, and Henry's law constant, KH, in the different mixtures studied thus obtaining an insight into the relative contribution of chemical and physical absorption of the gas. It is shown that chemical sorption proceeds through a 1 : 2 stoichiometry between CO2 and acetate-based ionic liquid. The presence of the C(CN)3- anion does not significantly affect the chemical reaction of the gas with the solvent (Keq = 75 ± 2 at 303 K) but leads to lower Henry's law constants (from KH = 77.8 ± 0.6 bar to KH = 49.5 ± 0.5 bar at 303 K), thus pointing towards larger physical absorption of the gas. The tricyanomethanide anion considerably improves the mass transfer by increasing the fluidity of the absorbent as proven by the larger diffusivities of all the ions when the concentration of the C(CN)3- anion increases in the mixtures.

  5. Computer Aided Solvent Selection and Design Framework

    DEFF Research Database (Denmark)

    Mitrofanov, Igor; Conte, Elisa; Abildskov, Jens

    in terms of: physical and chemical properties (solvent-pure properties); Environment, Health and Safety (EHS) characteristic (solvent-EHS properties); operational properties (solvent–solute properties). 3. Performing the search. The search step consists of two stages. The first is a generation and property......, the API molecule can be described in terms of conceptual segments (first step of the method) and, then, the solvent power of the pure solvents can be computed and ranked from the best to the worst (anti-solvent). Hence, the design of a solvent mixture that enhances the API solubility can be performed...... for organic synthesis. This part uses the solvent selection methodology of Gani et al. [4,5], which has been extended to handle multi-step chemical syntheses as well as solvent substitution for specific reaction steps in existing processes. The methodology for organic synthesis accordingly involves five steps...

  6. Two polyoxometallate-based supramolecular compounds influenced by the ratio between the polyoxometallate anion and organic cation.

    Science.gov (United States)

    Zhang, Qian; Liu, Jie; Lu, Jing; Gong, Shu-Wen

    2013-06-01

    Two polyoxometallate-based compounds, tris[1,1'-(butane-1,4-diyl)bis(1H-imidazol-3-ium)] bis[tetracosa-μ2-oxido-dodecaoxido-μ12-phosphato-dodecamolybdenum(VI)], (C10H16N4)3[PMo12O40]2, (I), and 1,1'-(butane-1,4-diyl)bis(1H-imidazol-3-ium) 1-[4-(1H-imidazol-1-yl)butyl]-1H-imidazol-3-ium tetracosa-μ2-oxido-dodecaoxido-μ12-phosphato-dodecamolybdenum(VI) dihydrate, (C10H16N4)(C10H15N4)[PMo12O40]·2H2O, (II), were synthesized by hydrothermal techniques at different pH values. The stoichiometric ratio between the polyoxometallate (POM) anions and organic cations is 2:3 in (I), with one of the cations lying on an inversion centre. The doubly protonated 1,1'-(butane-1,4-diyl)diimidazole (BIM) cations are linked to the [PMo12O40](3-) anions by hydrogen bonds to form a three-dimensional supramolecular network. The stoichiometric ratio of POM anions and organic cations is 1:2 in (II), and the anion is located about a centre of inversion. The partly protonated BIM cations and solvent water molecules form hydrogen bonds with the [PMo12O40](3-) anions, yielding a two-dimensional supramolecular layer. The different lattice architectures of (I) and (II) may be governed by the ratio between the POM anions and organic cations, which, in turn, is determined by the pH value.

  7. Photoelectron imaging of cyanovinylidene and cyanoacetylene anions.

    Science.gov (United States)

    Goebbert, Daniel J; Khuseynov, Dmitry; Sanov, Andrei

    2010-02-18

    Negative ions of cyanoacetylene and cyanovinylidene are generated simultaneously via the competing 1,1-H(2)(+) and 1,2-H(2)(+) abstraction channels of O(-) reaction with acrylonitrile. The two stable isomeric forms of the anion, CCHCN(-) and HCCCN(-), are separated by a large (approximately 2 eV) potential energy barrier. Their photodetachment provides access to both the reactant and the product sides of the neutral cyanovinylidene --> cyanoacetylene rearrangement reaction, predicted to involve only a very small barrier. Using photoelectron imaging spectroscopy at 532 and 355 nm, the adiabatic electron affinity of the reactive intermediate :C horizontal lineCHCN (X(1)A'), is determined to be 1.84 +/- 0.01 eV. The photoelectron spectrum of CCHCN(-) exhibits a vibrational progression attributed to the excitation of the CCH bending mode. The observed spectral features are reproduced reasonably well using a Franck-Condon simulation under the parallel-mode approximation. In contrast to unsubstituted acetylene, cyanoacetylene has a stable anionic state, which is adiabatically weakly bound, but has an experimentally determined vertical detachment energy of 1.04 +/- 0.05 eV. This measurement, along with the broad, structureless photoelectron spectrum of HCCCN(-) (with no identifiable origin), reflects the large geometry difference between the w-shaped structure of the anion and the linear equilibrium geometry of HCCCN.

  8. Water permeation through anion exchange membranes

    Science.gov (United States)

    Luo, Xiaoyan; Wright, Andrew; Weissbach, Thomas; Holdcroft, Steven

    2018-01-01

    An understanding of water permeation through solid polymer electrolyte (SPE) membranes is crucial to offset the unbalanced water activity within SPE fuel cells. We examine water permeation through an emerging class of anion exchange membranes, hexamethyl-p-terphenyl poly (dimethylbenzimidazolium) (HMT-PMBI), and compare it against series of membrane thickness for a commercial anion exchange membrane (AEM), Fumapem® FAA-3, and a series of proton exchange membranes, Nafion®. The HMT-PMBI membrane is found to possess higher water permeabilities than Fumapem® FAA-3 and comparable permeability than Nafion (H+). By measuring water permeation through membranes of different thicknesses, we are able to decouple, for the first time, internal and interfacial water permeation resistances through anion exchange membranes. Permeation resistances on liquid/membrane interface is found to be negligible compared to that for vapor/membrane for both series of AEMs. Correspondingly, the resistance of liquid water permeation is found to be one order of magnitude smaller compared to that of vapor water permeation. HMT-PMBI possesses larger effective internal water permeation coefficient than both Fumapem® FAA-3 and Nafion® membranes (60 and 18% larger, respectively). In contrast, the effective interfacial permeation coefficient of HMT-PMBI is found to be similar to Fumapem® (±5%) but smaller than Nafion®(H+) (by 14%).

  9. Revisiting the Anionic Polymerization of Methyl Ethacrylate

    Energy Technology Data Exchange (ETDEWEB)

    Kennemur, Justin G. [Department of Chemistry and Biochemistry, Florida State University, Tallahassee FL 32306-4390 USA; Bates, Frank S. [Department of Chemical Engineering and Materials Science, University of Minnesota, Minneapolis MN 55455-0431 USA; Hillmyer, Marc A. [Department of Chemistry, University of Minnesota, Minneapolis MN 55455-0431 USA

    2017-09-26

    Synthesis of poly(methyl ethacrylate), (PMEA), in tetrahydrofuran at -78 °C using anionic polymerization techniques results in high molar mass (>30 kg mol-1), low dispersity (1.3), and high conversion (>81%). The molar masses of a series of samples are consistent with values anticipated by the monomer-to-initiator ratio and conversion. These results represent a significant improvement to earlier reported attempts to prepare PMEA using anionic methods. Successful diblock polymerization of polystyrene-block-PMEA, (PS-PMEA), and poly(4-tert-butylstyrene)-block-PMEA, (PtBS-PMEA), is achieved through sequential anionic polymerization techniques with dispersities as low as 1.06 and segment molar fractions close to those targeted. Broad principal scattering peaks observed by small-angle X-ray scattering (SAXS) for symmetric PS-PMEA at relatively high molar mass (39 kg mol-1) suggests an effective interaction parameter (χeff) that is smaller than for PS-block-poly(methyl methacrylate). On the other hand, PtBS-PMEA block polymers form a well-ordered morphology based on SAXS measurements and is attributable to the more hydrophobic PtBS segment. These results confirm the viability of PMEA as a new constituent in the expanding suite of polymers suitable for preparing nanostructured block polymers.

  10. Sleep disturbances and exposure to organic solvents

    Energy Technology Data Exchange (ETDEWEB)

    Lindelof, B.; Almkvist, O.; Goethe, C. (Huddinge Hospital (Sweden))

    An inquiry about sleep habits and sleep disturbances revealed a significantly higher prevalence of insomnia in a solvent-exposed group than in a comparable group that had no occupational exposure to organic solvents. The solvent-exposed group has also registered an increased consumption of hypnotics, and a significant increase occurred in the number of individuals who had consulted physicians because of sleep disorders. The results indicate that solvent exposure could induce sleep disturbances.

  11. A new desorption method for removing organic solvents from activated carbon using surfactant.

    Science.gov (United States)

    Hinoue, Mitsuo; Ishimatsu, Sumiyo; Fueta, Yukiko; Hori, Hajime

    2017-03-28

    A new desorption method was investigated, which does not require toxic organic solvents. Efficient desorption of organic solvents from activated carbon was achieved with an ananionic surfactant solution, focusing on its washing and emulsion action. Isopropyl alcohol (IPA) and methyl ethyl ketone (MEK) were used as test solvents. Lauryl benzene sulfonic acid sodium salt (LAS) and sodium dodecyl sulfate (SDS) were used as the surfactant. Activated carbon (100 mg) was placed in a vial and a predetermined amount of organic solvent was added. After leaving for about 24 h, a predetermined amount of the surfactant solution was added. After leaving for another 72 h, the vial was heated in an incubator at 60°C for a predetermined time. The organic vapor concentration was then determined with a frame ionization detector (FID)-gas chromatograph and the desorption efficiency was calculated. A high desorption efficiency was obtained with a 10% surfactant solution (LAS 8%, SDS 2%), 5 ml desorption solution, 60°C desorption temperature, and desorption time of over 24 h, and the desorption efficiency was 72% for IPA and 9% for MEK. Under identical conditions, the desorption efficiencies for another five organic solvents were investigated, which were 36%, 3%, 32%, 2%, and 3% for acetone, ethyl acetate, dichloromethane, toluene, and m-xylene, respectively. A combination of two anionic surfactants exhibited a relatively high desorption efficiency for IPA. For toluene, the desorption efficiency was low due to poor detergency and emulsification power.

  12. Organic solvents in electromembrane extraction: recent insights

    DEFF Research Database (Denmark)

    Huang, Chuixiu; Gjelstad, Astrid; Pedersen-Bjergaard, Stig

    2016-01-01

    articles with focus on EME have been published. The current review summarizes the performance of EME with different organic solvents and discusses several criteria for efficient solvents in EME. In addition, the authors highlight their personal perspective about the most promising organic solvents for EME...

  13. Solvent Extraction of Furfural From Biomass

    Science.gov (United States)

    Humphrey, M. F.

    1984-01-01

    Solvent-extraction method reduces energy required to remove furfural produced during acid hydrolysis of biomass. Acid hydrolysis performed in vessel containing both solvents and reacting ingredients. With intimate contact between solvents and aqueous hydrolyis liqour, furfural removed form liquor almost as fast as it forms.

  14. CH-anion versus anion-π interactions in the crystal and in solution of pentafluorobenzyl phosphonium salts.

    Science.gov (United States)

    Müller, Michael; Albrecht, Markus; Sackmann, Johannes; Hoffmann, Andreas; Dierkes, Fiete; Valkonen, Arto; Rissanen, Kari

    2010-12-21

    A series of phosphonium salts with pentafluorobenzyl substituents have been synthesized and were investigated in the crystal as well as in solution. The solid state structures of 1a, 1b and 2d reveal the presence of anion-π as well as CH-anion interactions. The two attractive, yet competitive forces seem to act in concert and a directing effect of the CH interaction on the relative position between anion and π-system is observed. The search for anion-π interactions in solution failed. Only CH-anion interactions proved to be important in solution.

  15. Using GC-FID to Quantify the Removal of 4-sec-Butylphenol from NGS Solvent by NaOH

    Energy Technology Data Exchange (ETDEWEB)

    Sloop, Jr., Frederick V. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Moyer, Bruce A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2014-12-01

    A caustic wash of the solvent used in the Next-Generation Caustic-Side Solvent Extraction (NG-CSSX) process was found to remove the modifier breakdown product 4-sec-butylphenol (SBP) with varying efficiency depending on the aqueous NaOH concentration. Recent efforts at ORNL have aimed at characterizing the flowsheet chemistry and reducing the technical uncertainties of the NG-CSSX process. One technical uncertainty has been the efficacy of caustic washing of the solvent for the removal of lipophilic anions, in particular, the efficient removal of SBP, an important degradation product of the solvent modifier, Cs-7SB. In order to make this determination, it was necessary to develop a sensitive and reliable analytical technique for the detection and quantitation of SBP. This report recounts the development of a GC-FID-based (Gas Chromatography Flame Ionization Detection) technique for analyzing SBP and the utilization of the technique to subsequently confirm the ability of the caustic wash to efficiently remove SBP from the Next Generation Solvent (NGS) used in NG-CSSX. In particular, the developed technique was used to monitor the amount of SBP removed from a simple solvent and the full NGS by contact with sodium hydroxide wash solutions over a range of concentrations. The results show that caustic washing removes SBP with effectively the same efficiency as it did in the original Caustic-Side Solvent Extraction (CSSX) process.

  16. Dowex anion exchanger-loaded-baker's yeast as bi-functionalized biosorbents for selective extraction of anionic and cationic mercury(II) species.

    Science.gov (United States)

    Mahmoud, Mohamed E; Yakout, Amr A; Osman, Maher M

    2009-05-30

    Dowex anion exchanger-immobilized-baker's yeast [Dae-yeast] were synthesized and potentially applied as environmental friendly biosorbents to evaluate the up-take process of anionic and cationic mercury(II) species as well as other metal ions. Optimization of mass ratio of Dowex anion exchanger versus yeast (1:1-1:10) in presence of various interacting buffer solutions (pH 4.0-9.0) was performed and evaluated. Surface modification of [Dae-yeast] was characterized by scanning electron microscopy (SEM) and infrared spectroscopy. The maximum metal biosorption capacity values of [Dae-yeast] towards mercury(II) were found in the range of 0.800-0.960, 0.840-0.950 and 0.730-0.900 mmol g(-1) in presence of buffer solutions pH 2.0, 4.0 and 7.0, respectively. Three possible and different mechanisms are proposed to account for the biosorption of mercury and mercuric species under these three buffering conditions based on ion exchange, ion pair and chelation interaction processes. Factors affecting biosorption of mercury from aqueous medium including the pH effect of aqueous solutions (1.0-7.0), shaking time (1-30 min) and interfering ions were se arched. The potential applications of modified biosorbents for selective biosorption and extraction of mercury from different real matrices including dental filling waste materials, industrial waste water samples and mercury lamp waste materials were also explored. The results denote to excellent percentage extraction values, from nitric acid as the dissolution solvent with a pH 2.0, as determined in the range of 90.77-97.91+/-3.00-5.00%, 90.00-93.40+/-4.00-5.00% and 92.31-100.00+/-3.00-4.00% for the three tested samples, respectively.

  17. Features of the adsorption of naproxen enantiomers on weak chiral anion-exchangers in nonlinear chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Asnin, Leonid [University of Tennessee, Knoxville (UTK); Kaczmarski, Krzysztof [University of Tennessee and Rzeszow University of Technology, Poland; Guiochon, Georges A [ORNL

    2008-01-01

    The retention mechanism of the enantiomers of naproxen on a Pirkle-type chiral stationary phase (CSP) was studied. This CSP is made of a porous silica grafted with quinidine carbamate. It can interact with the weak organic electrolyte naproxen either by adsorbing it or by ion-exchange. Using frontal chromatography, we explored the adsorption equilibrium under such experimental conditions that naproxen dissociates or cannot dissociate. Under conditions preventing ionic dissociation, the adsorption isotherms were measured, the adsorption energy distributions determined, and the chromatographic profiles calculated. Three different types of the adsorption sites were found for both enantiomers. The density and the binding energy of these sites depend on the nature of the organic modifier. Different solute species, anions, neutral molecules, solvent-ion associates, and solute dimers can coexist in solution, giving rise to different forms of adsorption. This study showed the unexpected occurrence of secondary steps in the breakthrough profiles of S-naproxen in the adsorption mode at high concentrations. Being enantioselective, this phenomenon was assumed to result from the association of solute molecules involving a chiral selector moiety. A multisite Langmuir adsorption model was used to calculate band profiles. Although this model accounts excellently for the experimental adsorption isotherms, it does not explain all the features of the breakthrough profiles. A comparison between the calculated and experimental profiles allowed useful conclusions concerning the effects of the adsorbate-adsorbate and adsorbate-solvent interactions on the adsorption mechanism.

  18. Anion recognition by simple chromogenic and chromo-fluorogenic salicylidene Schiff base or reduced-Schiff base receptors.

    Science.gov (United States)

    Dalapati, Sasanka; Jana, Sankar; Guchhait, Nikhil

    2014-08-14

    This review contains extensive application of anion sensing ability of salicylidene type Schiff bases and their reduced forms having various substituents with respect to phenolic OH group. Some of these molecular systems behave as receptor for recognition or sensing of various anions in organic or aqueous-organic binary solvent mixture as well as in the solid supported test kits. Development of Schiff base or reduced Schiff base receptors for anion recognition event is commonly based on the theory of hydrogen bonding interaction or deprotonation of phenolic -OH group. The process of charge transfer (CT) or inhibition of excited proton transfer (ESIPT) or followed by photo-induced electron transfer (PET) lead to naked-eye color change, UV-vis spectral change, chemical shift in the NMR spectra and fluorescence spectral modifications. In this review we have tried to discuss about the anion sensing properties of Schiff base or reduced Schiff base receptors. Copyright © 2014 Elsevier B.V. All rights reserved.

  19. Potentiometric investigation of acid dissociation and anionic homoconjugation equilibria of substituted phenols in dimethyl sulfoxide[Substituted phenols; Acid-base equilibria; Dimethyl sulfoxide (DMSO); Potentiometry

    Energy Technology Data Exchange (ETDEWEB)

    Czaja, Malgorzata; Kozak, Anna; Makowski, Mariusz; Chmurzynski, Lech. E-mail: lech@chemik.chem.univ.gda.pl

    2003-10-01

    Standard acidity constants, K{sub a}{sup DMSO} (HA), expressed as pK{sub a}{sup DMSO} (HA) values, and anionic homoconjugation constants, K{sup DMSO}{sub AHA{sup -}}, (in the form of lg K{sup DMSO}{sub AHA{sup -}} values) have been determined for 11 substituted phenol-phenolate systems a polar protophilic aprotic solvent, dimethyl sulfoxide (DMSO) with a potentiometric titration. A linear relationship has been determined between lg K{sup DMSO}{sub AHA{sup -}} and pK{sub a}{sup DMSO} (HA). The tendency towards anionic homoconjugation in these systems increases with increasing pK{sub a}{sup DMSO} (HA) that is with declining phenol acidity. The pK{sub a}{sup DMSO} (HA) are correlated with both pK{sub a}{sup W} (HA) water and other polar non-aqeous solvents.

  20. Solvent cleaning system and method for removing contaminants from solvent used in resin recycling

    Science.gov (United States)

    Bohnert, George W [Harrisonville, MO; Hand, Thomas E [Lee's Summit, MO; DeLaurentiis, Gary M [Jamestown, CA

    2009-01-06

    A two step solvent and carbon dioxide based system that produces essentially contaminant-free synthetic resin material and which further includes a solvent cleaning system for periodically removing the contaminants from the solvent so that the solvent can be reused and the contaminants can be collected and safely discarded in an environmentally safe manner.

  1. Regulation of Autophagy-Related Protein and Cell Differentiation by High Mobility Group Box 1 Protein in Adipocytes

    Directory of Open Access Journals (Sweden)

    Huanhuan Feng

    2016-01-01

    Full Text Available High mobility group box 1 protein (HMGB1 is a molecule related to the development of inflammation. Autophagy is vital to maintain cellular homeostasis and protect against inflammation of adipocyte injury. Our recent work focused on the relationship of HMGB1 and autophagy in 3T3-L1 cells. In vivo experimental results showed that, compared with the normal-diet group, the high-fat diet mice displayed an increase in adipocyte size in the epididymal adipose tissues. The expression levels of HMGB1 and LC3II also increased in epididymal adipose tissues in high-fat diet group compared to the normal-diet mice. The in vitro results indicated that HMGB1 protein treatment increased LC3II formation in 3T3-L1 preadipocytes in contrast to that in the control group. Furthermore, LC3II formation was inhibited through HMGB1 knockdown by siRNA. Treatment with the HMGB1 protein enhanced LC3II expression after 2 and 4 days but decreased the expression after 8 and 10 days among various differentiation stages of adipocytes. By contrast, FABP4 expression decreased on the fourth day and increased on the eighth day. Hence, the HMGB1 protein modulated autophagy-related proteins and lipid-metabolism-related genes in adipocytes and could be a new target for treatment of obesity and related metabolic diseases.

  2. Overexpression of Receptor for Advanced Glycation End Products and High-Mobility Group Box 1 in Human Dental Pulp Inflammation

    Directory of Open Access Journals (Sweden)

    Salunya Tancharoen

    2014-01-01

    Full Text Available High mobility group box 1 (HMGB1, a nonhistone DNA-binding protein, is released into the extracellular space and promotes inflammation. HMGB1 binds to related cell signaling transduction receptors, including receptor for advanced glycation end products (RAGE, which actively participate in vascular and inflammatory diseases. The aim of this study was to examine whether RAGE and HMGB1 are involved in the pathogenesis of pulpitis and investigate the effect of Prevotella intermedia (P. intermedia lipopolysaccharide (LPS on RAGE and HMGB1 expression in odontoblast-like cells (OLC-1. RAGE and HMGB1 expression levels in clinically inflamed dental pulp were higher than those in healthy dental pulp. Upregulated expression of RAGE was observed in odontoblasts, stromal pulp fibroblasts-like cells, and endothelial-like cell lining human pulpitis tissue. Strong cytoplasmic HMGB1 immunoreactivity was noted in odontoblasts, whereas nuclear HMGB1 immunoreactivity was seen in stromal pulp fibroblasts-like cells in human pulpitis tissue. LPS stimulated OLC-1 cells produced HMGB1 in a dose-dependent manner through RAGE. HMGB1 translocation towards the cytoplasm and secretion from OLC-1 in response to LPS was inhibited by TPCA-1, an inhibitor of NF-κB activation. These findings suggest that RAGE and HMGB1 play an important role in the pulpal immune response to oral bacterial infection.

  3. Necrotic enlargement of cone photoreceptor cells and the release of high-mobility group box-1 in retinitis pigmentosa

    Science.gov (United States)

    Murakami, Y; Ikeda, Y; Nakatake, S; Tachibana, T; Fujiwara, K; Yoshida, N; Notomi, S; Nakao, S; Hisatomi, T; Miller, J W; Vavvas, DG; Sonoda, KH; Ishibashi, T

    2015-01-01

    Retinitis pigmentosa (RP) refers to a group of inherited retinal degenerations resulting form rod and cone photoreceptor cell death. The rod cell death due to deleterious genetic mutations has been shown to occur mainly through apoptosis, whereas the mechanisms and features of the secondary cone cell death have not been fully elucidated. Our previous study showed that the cone cell death in rd10 mice, an animal model of RP, involves necrotic features and is partly mediated by the receptor interacting protein kinase. However, the relevancy of necrotic cone cell death in human RP patients remains unknown. In the present study, we showed that dying cone cells in rd10 mice exhibited cellular enlargement, along with necrotic changes such as cellular swelling and mitochondrial rupture. In human eyes, live imaging of cone cells by adaptive optics scanning laser ophthalmoscopy revealed significantly increased percentages of enlarged cone cells in the RP patients compared with the control subjects. The vitreous of the RP patients contained significantly higher levels of high-mobility group box-1, which is released extracellularly associated with necrotic cell death. These findings suggest that necrotic enlargement of cone cells is involved in the process of cone degeneration, and that necrosis may be a novel target to prevent or delay the loss of cone-mediated central vision in RP. PMID:27551484

  4. High mobility conduction at (110) and (111) LaAlO3/SrTiO3 interfaces.

    Science.gov (United States)

    Herranz, G; Sánchez, F; Dix, N; Scigaj, M; Fontcuberta, J

    2012-01-01

    In recent years, striking discoveries have revealed that two-dimensional electron liquids (2DEL) confined at the interface between oxide band-insulators can be engineered to display a high mobility transport. The recognition that only few interfaces appear to suit hosting 2DEL is intriguing and challenges the understanding of these emerging properties not existing in bulk. Indeed, only the neutral TiO(2) surface of (001)SrTiO(3) has been shown to sustain 2DEL. We show that this restriction can be surpassed: (110) and (111) surfaces of SrTiO(3) interfaced with epitaxial LaAlO(3) layers, above a critical thickness, display 2DEL transport with mobilities similar to those of (001)SrTiO(3). Moreover we show that epitaxial interfaces are not a prerequisite: conducting (110) interfaces with amorphous LaAlO(3) and other oxides can also be prepared. These findings open a new perspective both for materials research and for elucidating the ultimate microscopic mechanism of carrier doping.

  5. Overexpression of Receptor for Advanced Glycation End Products and High-Mobility Group Box 1 in Human Dental Pulp Inflammation

    Science.gov (United States)

    Tancharoen, Salunya; Tengrungsun, Tassanee; Suddhasthira, Theeralaksna; Kikuchi, Kiyoshi; Vechvongvan, Nuttavun; Maruyama, Ikuro

    2014-01-01

    High mobility group box 1 (HMGB1), a nonhistone DNA-binding protein, is released into the extracellular space and promotes inflammation. HMGB1 binds to related cell signaling transduction receptors, including receptor for advanced glycation end products (RAGE), which actively participate in vascular and inflammatory diseases. The aim of this study was to examine whether RAGE and HMGB1 are involved in the pathogenesis of pulpitis and investigate the effect of Prevotella intermedia (P. intermedia) lipopolysaccharide (LPS) on RAGE and HMGB1 expression in odontoblast-like cells (OLC-1). RAGE and HMGB1 expression levels in clinically inflamed dental pulp were higher than those in healthy dental pulp. Upregulated expression of RAGE was observed in odontoblasts, stromal pulp fibroblasts-like cells, and endothelial-like cell lining human pulpitis tissue. Strong cytoplasmic HMGB1 immunoreactivity was noted in odontoblasts, whereas nuclear HMGB1 immunoreactivity was seen in stromal pulp fibroblasts-like cells in human pulpitis tissue. LPS stimulated OLC-1 cells produced HMGB1 in a dose-dependent manner through RAGE. HMGB1 translocation towards the cytoplasm and secretion from OLC-1 in response to LPS was inhibited by TPCA-1, an inhibitor of NF-κB activation. These findings suggest that RAGE and HMGB1 play an important role in the pulpal immune response to oral bacterial infection. PMID:25114379

  6. Nickel resistance and chromatin condensation in Saccharomyces cerevisiae expressing a maize high mobility group I/Y protein.

    Science.gov (United States)

    Forzani, C; Loulergue, C; Lobréaux, S; Briat, J F; Lebrun, M

    2001-05-18

    Expression of a maize cDNA encoding a high mobility group (HMG) I/Y protein enables growth of transformed yeast on a medium containing toxic nickel concentrations. No difference in the nickel content was measured between yeast cells expressing either the empty vector or the ZmHMG I/Y2 cDNA. The ZmHMG I/Y2 protein contains four AT hook motifs known to be involved in binding to the minor groove of AT-rich DNA regions. HMG I/Y proteins may act as architectural elements modifying chromatin structure. Indeed, a ZmHMG I/Y2-green fluorescent protein fusion protein was observed in yeast nuclei. Nickel toxicity has been suggested to occur through an epigenetic mechanism related to chromatin condensation and DNA methylation, leading to the silencing of neighboring genes. Therefore, the ZmHMG I/Y2 protein could prevent nickel toxicity by interfering with chromatin structure. Yeast cell growth in the presence of nickel and yeast cells expressing the ZmHMG I/Y2 cDNA increased telomeric URA3 gene silencing. Furthermore, ZmHMG I/Y2 restored a wild-type level of nickel sensitivity to the yeast (Delta)rpd3 mutant. Therefore, nickel resistance of yeast cells expressing the ZmHMG I/Y2 cDNA is likely achieved by chromatin structure modification, restricting nickel accessibility to DNA.

  7. Correlation between Serum Levels of High Mobility Group Box-1 Protein and Pancreatitis: A Meta-Analysis

    Directory of Open Access Journals (Sweden)

    Yan Lin

    2015-01-01

    Full Text Available Background. Aberrant expression of high mobility group box-1 protein (HMGB1 contributes to the progression of various inflammatory diseases. This meta-analysis focused on the clinical significance of serum HMGB1 levels in pancreatitis patients, with the goal of building a novel diagnostic score model. Method. We conducted a meta-analysis by searching in the PubMed, Embase, Web of Science, Cochrane Library, CISCOM, CINAHL, Google Scholar, China BioMedicine (CBM, and China National Knowledge Infrastructure (CNKI databases without any language restrictions. Studies were pooled and standard mean difference (SMD and its corresponding 95% confidence intervals (95% CIs were calculated. Version 12.0 STATA software was used for statistical analysis. Results. We performed a final analysis of 841 subjects from 12 clinical case-control studies. The meta-analysis results showed a positive association between serum HMGB1 levels and the progression of pancreatitis. In the subgroup analysis by country, high serum level of HMGB1 may be related to pancreatitis progression in China, Korea, Hungary, and Japan populations (all P<0.05. Conclusion. The present meta-analysis indicated that serum HMGB1 level was statistically elevated in patients with pancreatitis, and thus serum levels of HMGB1 could be determined to be a useful biomarker for pancreatitis patients.

  8. Contribution of high-mobility group box-1 to the development of ventilator-induced lung injury.

    Science.gov (United States)

    Ogawa, Eileen N; Ishizaka, Akitoshi; Tasaka, Sadatomo; Koh, Hidefumi; Ueno, Hiroshi; Amaya, Fumimasa; Ebina, Masahito; Yamada, Shingo; Funakoshi, Yosuke; Soejima, Junko; Moriyama, Kiyoshi; Kotani, Toru; Hashimoto, Satoru; Morisaki, Hiroshi; Abraham, Edward; Takeda, Junzo

    2006-08-15

    Proinflammatory cytokines play an important role in ventilator-induced lung injury (VILI). High-mobility group box-1 (HMGB1) is a macrophage-derived proinflammatory cytokine that can cause lung injury. This study tested the hypothesis that HMGB1 is released in intact lungs ventilated with large Vt. A second objective was to identify the source of HMGB1. A third objective was to examine the effects of blocking HMGB1 on the subsequent development of VILI. Bronchoalveolar lavage fluid (BALF) and lung tissues were obtained from rabbits mechanically ventilated for 4 h with a small (8 ml/kg) versus a large (30 ml/kg) Vt. BALF was also obtained from rabbits with intratracheal instillation of anti-HMGB1 antibody before the initiation of large Vt ventilation. The concentrations of HMGB1 in BALF were fivefold higher in the large than in the small Vt group. Immunohistochemistry and immunofluorescence studies revealed expression of HMGB1 in the cytoplasm of macrophages and neutrophils in lungs ventilated with large Vt. Blocking HMGB1 improved oxygenation, limited microvascular permeability and neutrophil influx into the alveolar lumen, and decreased concentrations of tumor necrosis factor-alpha in BALF. These observations suggest that HMGB1 could be one of the deteriorating factors in the development of VILI.

  9. Activation of Plant Innate Immunity by Extracellular High Mobility Group Box 3 and Its Inhibition by Salicylic Acid.

    Directory of Open Access Journals (Sweden)

    Hyong Woo Choi

    2016-03-01

    Full Text Available Damage-associated molecular pattern molecules (DAMPs signal the presence of tissue damage to induce immune responses in plants and animals. Here, we report that High Mobility Group Box 3 (HMGB3 is a novel plant DAMP. Extracellular HMGB3, through receptor-like kinases BAK1 and BKK1, induced hallmark innate immune responses, including i MAPK activation, ii defense-related gene expression, iii callose deposition, and iv enhanced resistance to Botrytis cinerea. Infection by necrotrophic B. cinerea released HMGB3 into the extracellular space (apoplast. Silencing HMGBs enhanced susceptibility to B. cinerea, while HMGB3 injection into apoplast restored resistance. Like its human counterpart, HMGB3 binds salicylic acid (SA, which results in inhibition of its DAMP activity. An SA-binding site mutant of HMGB3 retained its DAMP activity, which was no longer inhibited by SA, consistent with its reduced SA-binding activity. These results provide cross-kingdom evidence that HMGB proteins function as DAMPs and that SA is their conserved inhibitor.

  10. Association between maternal serum high mobility group box 1 levels and pregnancy complicated by gestational diabetes mellitus.

    Science.gov (United States)

    Giacobbe, A; Granese, R; Grasso, R; Salpietro, V; Corrado, F; Giorgianni, G; Foti, G; Amadore, D; Triolo, O; Giunta, L; Di Benedetto, A

    2016-05-01

    Gestational diabetes mellitus (GDM), is characterized by chronic, low-grade subclinical inflammation with altered production of cytokines and mediators. Recently, a new protein acting as a "danger signal", high mobility group box 1 (HMGB1), that migrates quickly during electrophoresis, has been identified. The aim of our study was to analyze serum levels of HMGB1 in pregnant women, with or without GDM, in the third trimester of pregnancy to evaluate correlation with insulin resistance and other risk factors for GDM. Seventy five pregnant women positive to the 75 g oral glucose tolerance test (OGTT) were included in the study group and 48 pregnant women who were negative to the screening test, were randomly selected using a computer-generated randomisation table. A significant positive univariate correlation was observed between serum HMGB1 levels, HOMA-IR index, glycaemia values at OGTT and pre-pregnancy BMI. Moreover, logistic regression analysis showed that serum HMGB1 was independent linked to GDM. Our study demonstrated that HMGB1, a marker of chronic inflammation, is associated to GDM and insulin resistance level, in the third trimester of pregnancy. Copyright © 2016 The Italian Society of Diabetology, the Italian Society for the Study of Atherosclerosis, the Italian Society of Human Nutrition, and the Department of Clinical Medicine and Surgery, Federico II University. Published by Elsevier B.V. All rights reserved.

  11. Role of the acidic tail of high mobility group protein B1 (HMGB1) in protein stability and DNA bending.

    Science.gov (United States)

    Belgrano, Fabricio S; de Abreu da Silva, Isabel C; Bastos de Oliveira, Francisco M; Fantappié, Marcelo R; Mohana-Borges, Ronaldo

    2013-01-01

    High mobility group box (HMGB) proteins are abundant nonhistone proteins found in all eukaryotic nuclei and are capable of binding/bending DNA. The human HMGB1 is composed of two binding motifs, known as Boxes A and B, are L-shaped alpha-helix structures, followed by a random-coil acidic tail that consists of 30 Asp and Glu residues. This work aimed at evaluating the role of the acidic tail of human HMGB1 in protein stability and DNA interactions. For this purpose, we cloned, expressed and purified HMGB1 and its tailless form, HMGB1ΔC, in E. coli strain. Tryptophan fluorescence spectroscopy and circular dichroism (CD) experiments clearly showed an increase in protein stability promoted by the acidic tail under different conditions, such as the presence of the chemical denaturant guanidine hydrochloride (Gdn.HCl), high temperature and low pH. Folding intermediates found at low pH for both proteins were denatured only in the presence of chemical denaturant, thus showing a relatively high stability. The acidic tail did not alter the DNA-binding properties of the protein, although it enhanced the DNA bending capability from 76° (HMGB1ΔC) to 91° (HMGB1), as measured using the fluorescence resonance energy transfer technique. A model of DNA bending in vivo was proposed, which might help to explain the interaction of HMGB1 with DNA and other proteins, i.e., histones, and the role of that protein in chromatin remodeling.

  12. Paraformaldehyde Fixation May Lead to Misinterpretation of the Subcellular Localization of Plant High Mobility Group Box Proteins.

    Science.gov (United States)

    Li, Man-Wah; Zhou, Liang; Lam, Hon-Ming

    2015-01-01

    Arabidopsis High Mobility Group Box (HMBG) proteins were previously found associated with the interphase chromatin but not the metaphase chromosome. However, these studies are usually based on immunolocalization analysis involving paraformaldehyde fixation. Paraformaldehyde fixation has been widely adapted to preserved cell morphology before immunofluorescence staining. On one hand, the processed cells are no longer living. On the other hand, the processing may lead to misinterpretation of localization. HMGBs from Arabidopsis were fused with enhanced green fluorescence protein (EGFP) and transformed into tobacco BY-2 cells. Basically, the localization of these HMGB proteins detected with EGFP fluorescence in interphase agreed with previous publications. Upon 4% paraformaldehyde fixation, AtHMGB1 was found associated with interphase but not the metaphase chromosomes as previously reported. However, when EGFP fluorescence signal was directly observed under confocal microscope without fixation, association of AtHMGB1 with metaphase chromosomes can be detected. Paraformaldehyde fixation led to dissociation of EGFP tagged AtHMBG1 protein from metaphase chromosomes. This kind of pre-processing of live specimen may lead to dissociation of protein-protein or protein-nucleic acid interaction. Therefore, using of EGFP fusion proteins in live specimen is a better way to determine the correct localization and interaction of proteins.

  13. The seabird paradox: dispersal, genetic structure and population dynamics in a highly mobile, but philopatric albatross species.

    Science.gov (United States)

    Milot, Emmanuel; Weimerskirch, Henri; Bernatchez, Louis

    2008-04-01

    The philopatric behaviour of albatrosses has intrigued biologists due to the high mobility of these seabirds. It is unknown how albatrosses maintain a system of fragmented populations without frequent dispersal movements, in spite of the long-term temporal heterogeneity in resource distribution at sea. We used both genetic (amplified fragment length polymorphism) and capture-mark-recapture (CMR) data to identify explicitly which among several models of population dynamics best applies to the wandering albatross (Diomedea exulans) and to test for migration-drift equilibrium. We previously documented an extremely low genetic diversity in this species. Here, we show that populations exhibit little genetic differentiation across the species' range (Theta(B) albatross. Yet, our data suggest that several other factors including ongoing gene flow, recurrent long-distance dispersal and source-sink dynamics have contributed to different extent in shaping the genetic signature observed in this species. Our results show that an absence of genetic structuring may in itself reveal little about the true population dynamics in seabirds, but can provide insights into important processes when a comparison with other information, such as demographic data, is possible.

  14. Time-Frequency Based Channel Estimation for High-Mobility OFDM Systems—Part II: Cooperative Relaying Case

    Directory of Open Access Journals (Sweden)

    Önen Erol

    2010-01-01

    Full Text Available We consider the estimation of time-varying channels for Cooperative Orthogonal Frequency Division Multiplexing (CO-OFDM systems. In the next generation mobile wireless communication systems, significant Doppler frequency shifts are expected the channel frequency response to vary in time. A time-invariant channel is assumed during the transmission of a symbol in the previous studies on CO-OFDM systems, which is not valid in high mobility cases. Estimation of channel parameters is required at the receiver to improve the performance of the system. We estimate the model parameters of the channel from a time-frequency representation of the received signal. We present two approaches for the CO-OFDM channel estimation problem where in the first approach, individual channels are estimated at the relay and destination whereas in the second one, the cascaded source-relay-destination channel is estimated at the destination. Simulation results show that the individual channel estimation approach has better performance in terms of MSE and BER; however it has higher computational cost compared to the cascaded approach.

  15. High-Mobility Group Box 1 Disrupts Metabolic Function with Cigarette Smoke Exposure in a Ceramide-Dependent Manner

    Directory of Open Access Journals (Sweden)

    Oliver J. Taylor

    2017-05-01

    Full Text Available We have previously found that cigarette smoke disrupts metabolic function, in part, by increasing muscle ceramide accrual. To further our understanding of this, we sought to determine the role of the cytokine high-mobility group box 1 (HMGB1, which is increased with smoke exposure, in smoke-induced muscle metabolic perturbations. To test this theory, we determined HMGB1 from lungs of human smokers, as well as from lung cells from mice exposed to cigarette smoke. We also treated cells and mice directly with HMGB1, in the presence or absence of myriocin, an inhibitor of serine palmitoyltransferase, the rate-limiting enzyme in ceramide biosynthesis. Outcomes included assessments of insulin resistance and muscle mitochondrial function. HMGB1 was significantly increased in both human lungs and rodent alveolar macrophages. Further testing revealed that HMGB1 treatment elicited a widespread increase in ceramide species and reduction in myotube mitochondrial respiration, an increase in reactive oxygen species, and reduced insulin-stimulated Akt phosphorylation. Inhibition of ceramide biosynthesis with myriocin was protective. In mice, by comparing treatments of HMGB1 injections with or without myriocin, we found that HMGB1 injections resulted in increased muscle ceramides, especially C16 and C24, which were necessary for reduced muscle mitochondrial respiration and compromised insulin and glucose tolerance. In conclusion, HMGB1 may be a necessary intermediate in the ceramide-dependent metabolic consequences of cigarette smoke exposure.

  16. Up-regulation of TLR2 and TLR4 in high mobility group Box1-stimulated macrophages in pulpitis patients

    Science.gov (United States)

    Mahmoudi, Javad; Sabermarouf, Babak; Baradaran, Behzad; Sadat-Hatamnezhad, Leila; Shotorbani, Siamak Sandoghchian

    2017-01-01

    Objective(s): High Mobility Group Box1 (HMGB1) is a nonhistone, DNA-binding protein that serves a crucial role in regulating gene transcription and is involved in a variety of proinflammatory, extracellular activities. The aim of this study was to explore whether HMGB1 stimulation can up-regulate the expression of Toll-like Receptor 2 (TLR2) and Toll-like Receptor 4 (TLR4) on macrophages from pulpitis and to clarify the subsequent events involving Th17 cells and Th17 cell-associated cytokine changes. Materials and Methods: Having prepared dental pulp tissues of pulpitis and healthy controls, macrophage were isolated and cultured. Macrophages were thereafter stimulated by HMGB1 time course. RT-QPCR, flowcytometer, immunofluorescence, Western blotting, and ELISA techniques were used in the present research. Results: Our results showed that the expression of TLR2 and TLR4 on macrophages stimulated with HMGB1 increased in pulpitis compared with controls (macrophages without HMGB1 stimulation) with a statistical significance (Ppulpitis increased, and NF-kB, the downstream target of TLR2 and TLR4, also showed a marked elevation after macrophages’ stimulation by HMGB1. Conclusion: The evidence from the present study suggests that the enhanced TLR2 and TLR4 pathways and Th17 cell polarization may be due to HMGB1 stimulation in pulpitis. PMID:28293399

  17. Effect of electron-electron interaction on cyclotron resonance in high-mobility InAs/AlSb quantum wells

    Energy Technology Data Exchange (ETDEWEB)

    Krishtopenko, S. S., E-mail: sergey.krishtopenko@mail.ru; Gavrilenko, V. I. [Institute for Physics of Microstructures, Russian Academy of Sciences, 603950 Nizhny Novgorod, GSP-105 (Russian Federation); Lobachevsky State University, 23 Prospekt Gagarina, 603950 Nizhny Novgorod (Russian Federation); Ikonnikov, A. V. [Institute for Physics of Microstructures, Russian Academy of Sciences, 603950 Nizhny Novgorod, GSP-105 (Russian Federation); Orlita, M. [Laboratoire National des Champs Magnétiques Intenses (LNCMI-G), CNRS, 25 rue des Martyrs, B.P. 166, 38042 Grenoble (France); Sadofyev, Yu. G. [P.N. Lebedev Physical Institute, Russian Academy of Sciences, Moscow 119991, GSP-1, 53 Leninskiy Prospect (Russian Federation); Goiran, M. [Laboratoire National des Champs Magnétiques Intenses (LNCMI-T), CNRS, 143 Avenue de Rangueil, 31400 Toulouse (France); Teppe, F.; Knap, W. [Laboratoire Charles Coulomb (L2C), UMR CNRS 5221, GIS-TERALAB, Universite Montpellier II, 34095 Montpellier (France)

    2015-03-21

    We report observation of electron-electron (e-e) interaction effect on cyclotron resonance (CR) in InAs/AlSb quantum well heterostructures. High mobility values allow us to observe strongly pronounced triple splitting of CR line at noninteger filling factors of Landau levels ν. At magnetic fields, corresponding to ν > 4, experimental values of CR energies are in good agreement with single-electron calculations on the basis of eight-band k ⋅ p Hamiltonian. In the range of filling factors 3 < ν < 4 pronounced, splitting of CR line, exceeding significantly the difference in single-electron CR energies, is discovered. The strength of the splitting increases when occupation of the partially filled Landau level tends to a half, being in qualitative agreement with previous prediction by MacDonald and Kallin [Phys. Rev. B 40, 5795 (1989)]. We demonstrate that such behaviour of CR modes can be quantitatively described if one takes into account both electron correlations and the mixing between conduction and valence bands in the calculations of matrix elements of e-e interaction.

  18. High-Mobility Group Box-1 Induces Decreased Brain-Derived Neurotrophic Factor-Mediated Neuroprotection in the Diabetic Retina

    Directory of Open Access Journals (Sweden)

    Ahmed M. Abu El-Asrar

    2013-01-01

    Full Text Available To test the hypothesis that brain-derived neurotrophic factor-(BDNF- mediated neuroprotection is reduced by high-mobility group box-1 (HMGB1 in diabetic retina, paired vitreous and serum samples from 46 proliferative diabetic retinopathy and 34 nondiabetic patients were assayed for BDNF, HMGB1, soluble receptor for advanced glycation end products (sRAGE, soluble intercellular adhesion molecule-1 (sICAM-1, monocyte chemoattractant protein-1 (MCP-1, and TBARS. We also examined retinas of diabetic and HMGB1 intravitreally injected rats. The effect of the HMGB1 inhibitor glycyrrhizin on diabetes-induced changes in retinal BDNF expressions was studied. Western blot, ELISA, and TBARS assays were used. BDNF was not detected in vitreous samples. BDNF levels were significantly lower in serum samples from diabetic patients compared with nondiabetics, whereas HMGB1, sRAGE, sICAM-1, and TBARS levels were significantly higher in diabetic serum samples. MCP-1 levels did not differ significantly. There was significant inverse correlation between serum levels of BDNF and HMGB1. Diabetes and intravitreal administration of HMGB1 induced significant upregulation of the expression of HMGB1, TBARS, and cleaved caspase-3, whereas the expression of BDNF and synaptophysin was significantly downregulated in rat retinas. Glycyrrhizin significantly attenuated diabetes-induced downregulation of BDNF. Our results suggest that HMGB1-induced downregulation of BDNF might be involved in pathogenesis of diabetic retinal neurodegeneration.

  19. Complex quantum transport in a modulation doped strained Ge quantum well heterostructure with a high mobility 2D hole gas

    Science.gov (United States)

    Morrison, C.; Casteleiro, C.; Leadley, D. R.; Myronov, M.

    2016-09-01

    The complex quantum transport of a strained Ge quantum well (QW) modulation doped heterostructure with two types of mobile carriers has been observed. The two dimensional hole gas (2DHG) in the Ge QW exhibits an exceptionally high mobility of 780 000 cm2/Vs at temperatures below 10 K. Through analysis of Shubnikov de-Haas oscillations in the magnetoresistance of this 2DHG below 2 K, the hole effective mass is found to be 0.065 m0. Anomalous conductance peaks are observed at higher fields which deviate from standard Shubnikov de-Haas and quantum Hall effect behaviour due to conduction via multiple carrier types. Despite this complex behaviour, analysis using a transport model with two conductive channels explains this behaviour and allows key physical parameters such as the carrier effective mass, transport, and quantum lifetimes and conductivity of the electrically active layers to be extracted. This finding is important for electronic device applications, since inclusion of highly doped interlayers which are electrically active, for enhancement of, for example, room temperature carrier mobility, does not prevent analysis of quantum transport in a QW.

  20. High-mobility group protein B1 (HMGB1) is a novel biomarker for human ovarian cancer.

    Science.gov (United States)

    Chen, Jie; Xi, Bo; Zhao, Yueran; Yu, Yang; Zhang, Jie; Wang, Chunyu

    2012-07-01

    High mobility group box l (HMGB1), a nuclear and extracellular protein, is implicated in some physiologic and pathologic conditions. In this study, we investigated the expression and function of HMGB1 in ovarian cancer. cDNA microarray analysis was performed to compare gene expression profiles of the highly invasive and the low invasive subclones derived from the SKOV3 human ovarian cancer cell line. Immunohistochemistry (IHC) staining was performed to investigate HMGB1 expression in a total of 100 ovarian tissue specimens. In functional assays, effects of HMGB1 knockdown on the biological behavior of ovarian cancer cells were investigated. HMGB1 was overexpressed in the highly invasive subclone compared with the low invasive subclone. High HMGB1 expression was associated with poor clinicopathologic features. Knockdown of HMGB1 expression significantly suppressed ovarian cancer cell proliferation accompanied by decreased cyclin D1 and PCNA expression, and inhibited cell migration and invasion accompanied by decreased MMP2 and MMP9 activities. HMGB1 is a newly identified gene overexpressed in ovarian cancer and associated with poor clinicopathologic features. HMGB1 may serve as a new biomarker and a therapeutic target for ovarian cancer in the future. Copyright © 2012 Elsevier Inc. All rights reserved.

  1. Expression of high mobility group box 1 in inflamed dental pulp and its chemotactic effect on dental pulp cells

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Xufang, E-mail: xufang.zhang@student.qut.edu.au [Department of Operative Dentistry and Endodontics, Guanghua School of Stomatology, Guangdong Province Key Laboratory of Stomatology, Sun Yat-sen University, Guangzhou 510055 (China); Institute of Health and Biomedical Innovation, Queensland University of Technology, Brisbane, QLD 4059 (Australia); Jiang, Hongwei, E-mail: jianghw@163.com [Department of Operative Dentistry and Endodontics, Guanghua School of Stomatology, Guangdong Province Key Laboratory of Stomatology, Sun Yat-sen University, Guangzhou 510055 (China); Gong, Qimei, E-mail: gongqmei@gmail.com [Department of Operative Dentistry and Endodontics, Guanghua School of Stomatology, Guangdong Province Key Laboratory of Stomatology, Sun Yat-sen University, Guangzhou 510055 (China); Fan, Chen, E-mail: c3.fan@student.qut.edu.au [Institute of Health and Biomedical Innovation, Queensland University of Technology, Brisbane, QLD 4059 (Australia); Huang, Yihua, E-mail: enu0701@163.com [Department of Operative Dentistry and Endodontics, Guanghua School of Stomatology, Guangdong Province Key Laboratory of Stomatology, Sun Yat-sen University, Guangzhou 510055 (China); Ling, Junqi, E-mail: lingjq@mail.sysu.edu.cn [Department of Operative Dentistry and Endodontics, Guanghua School of Stomatology, Guangdong Province Key Laboratory of Stomatology, Sun Yat-sen University, Guangzhou 510055 (China)

    2014-08-08

    Highlights: • HMGB1 translocated from nucleus to cytoplasm during dental pulp inflammation. • HMGB1and its receptor RAGE were up-regulated in hDPCs under LPS stimulation. • HMGB1 enhanced hDPCs migration and induces cytoskeleton reorganization. • HMGB1 may play a critical role in dental pulp repair during inflamed state. - Abstract: High mobility group box 1 protein (HMGB1) is a chromatin protein which can be released extracellularly, eliciting a pro-inflammatory response and promoting tissue repair process. This study aimed to examine the expression and distribution of HMGB1 and its receptor RAGE in inflamed dental pulp tissues, and to assess its effects on proliferation, migration and cytoskeleton of cultured human dental pulp cells (DPCs). Our data demonstrated that cytoplasmic expression of HMGB1 was observed in inflamed pulp tissues, while HMGB1 expression was confined in the nuclei in healthy dental pulp. The mRNA expression of HMGB1 and RAGE were significantly increased in inflamed pulps. In in vitro cultured DPCs, expression of HMGB1 in both protein and mRNA level was up-regulated after treated with lipopolysaccharide (LPS). Exogenous HMGB1 enhanced DPCs migration in a dose-dependent manner and induced the reorganization of f-actin in DPCs. Our results suggests that HMGB1 are not only involved in the process of dental pulp inflammation, but also play an important role in the recruitment of dental pulp stem cells, promoting pulp repair and regeneration.

  2. Academic achievement of homeless and highly mobile children in an urban school district: longitudinal evidence on risk, growth, and resilience.

    Science.gov (United States)

    Obradović, Jelena; Long, Jeffrey D; Cutuli, J J; Chan, Chi-Keung; Hinz, Elizabeth; Heistad, David; Masten, Ann S

    2009-01-01

    Longitudinal growth trajectories of reading and math achievement were studied in four primary school grade cohorts (GCs) of a large urban district to examine academic risk and resilience in homeless and highly mobile (H/HM) students. Initial achievement was assessed when student cohorts were in the second, third, fourth, and fifth grades, and again 12 and 18 months later. Achievement trajectories of H/HM students were compared to low-income but nonmobile students and all other tested students in the district, controlling for four well-established covariates of achievement: sex, ethnicity, attendance, and English language skills. Both disadvantaged groups showed markedly lower initial achievement than their more advantaged peers, and H/HM students manifested the greatest risk, consistent with an expected risk gradient. Moreover, in some GCs, both disadvantaged groups showed slower growth than their relatively advantaged peers. Closer examination of H/HM student trajectories in relation to national test norms revealed striking variability, including cases of academic resilience as well as problems. H/HM students may represent a major component of "achievement gaps" in urban districts, but these students also constitute a heterogeneous group of children likely to have markedly diverse educational needs. Efforts to close gaps or enhance achievement in H/HM children require more differentiated knowledge of vulnerability and protective processes that may shape individual development and achievement.

  3. Solvent and electrolyte effects in PPyDBS free standing films

    Science.gov (United States)

    Kiefer, Rudolf; Martinez, Jose G.; Otero, Toribio F.; Kesküla, Arko; Kaasik, Friedrich; Harjo, Madis; Valner, Robert; Vaddepally, Vishwaja; Peikolainen, Anna-Liisa; Aabloo, Alvo

    2015-04-01

    Free standing conducting polymer films based on polypyrrole doped with dodecylbenzoesulfate (PPyDBS) are investigated in TBACF3SO3 (tetrabutylammonium trifluoromethanesulfonate) propylene carbonate (PC-Tf) followed in aqueous TMACl tetramethylammonium chloride (Aq-TM) with the aim to investigate actuation properties (anion or cation-driven actuation). Under isometric (constant force) conditions ECMD (electro-chemo-mechanical deformation) measurements are performed during cyclic voltammetric and chronoamperometric experiments. Electrolyte and solvent effects revealing that the actuation direction in propylene carbonate electrolyte changed from expansion at anodic potential to expansion at cathodic potentials during square wave potential steps. Finally if the PPyDBS film immersed in aqueous electrolyte the anion-driven actuation properties are maintenance. SEM measurements are implemented to reefer changes in film morphology and ion content (EDX, energy dispersive X-Ray) before and after actuation.

  4. Enrichment of copper and recycling of cyanide from copper-cyanide waste by solvent extraction

    Science.gov (United States)

    Gao, Teng-yue; Liu, Kui-ren; Han, Qing; Xu, Bin-shi

    2016-11-01

    The enrichment of copper from copper-cyanide wastewater by solvent extraction was investigated using a quaternary ammonium salt as an extractant. The influences of important parameters, e.g., organic-phase components, aqueous pH values, temperature, inorganic anion impurities, CN/Cu molar ratio, and stripping reagents, were examined systematically, and the optimal conditions were determined. The results indicated that copper was effectively concentrated from low-concentration solutions using Aliquat 336 and that the extraction efficiency increased linearly with increasing temperature. The aqueous pH value and concentrations of inorganic anion impurities only weakly affected the extraction process when varied in appropriate ranges. The CN/Cu molar ratio affected the extraction efficiency by changing the distribution of copper-cyanide complexes. The difference in gold leaching efficiency between using raffinate and fresh water was negligible.

  5. High mobility group box 1 levels are not associated with subclinical carotid atherosclerosis in patients with granulomatosis with polyangiitis but are reduced by glucocorticoids and statins

    NARCIS (Netherlands)

    Silva de Souza, Alexandre; De Leeuw, Karina; Westra, Johanna; Smit, Andries J.; Van Der Graaf, Anne Marijn; Nienhuis, Hans L.A.; Bijzet, Johan; Limburg, Pieter C.; Stegeman, Coen A.; Bijl, Marc; Kallenberg, Cees G.M.

    2012-01-01

    Background/Purpose: High mobility group box 1 (HMGB1) is a non-histone DNA binding protein that is passively released by dying cells or actively secreted by immunocompetent cells and the receptor for advanced glycation end-products (RAGE) is one of its receptors. Higher levels of HMGB1 have been

  6. High-mobility group box 1 and the receptor for advanced glycation end products contribute to lung injury during Staphylococcus aureus pneumonia

    NARCIS (Netherlands)

    Achouiti, Ahmed; van der Meer, Anne Jan; Florquin, Sandrine; Yang, Huan; Tracey, Kevin J.; van 't Veer, Cornelis; de Vos, Alex F.; van der Poll, Tom

    2013-01-01

    Staphylococcus (S.) aureus has emerged as an important cause of necrotizing pneumonia. Lung injury during S. aureus pneumonia may be enhanced by local release of damage associated molecular patterns such as high-mobility group box 1 (HMGB1). In the current study we sought to determine the functional

  7. Preparation of Two-Layer Anion-Exchange Poly(ethersulfone Based Membrane: Effect of Surface Modification

    Directory of Open Access Journals (Sweden)

    Lucie Zarybnicka

    2016-01-01

    Full Text Available The present work deals with the surface modification of a commercial microfiltration poly(ethersulfone membrane by graft polymerization technique. Poly(styrene-co-divinylbenzene-co-4-vinylbenzylchloride surface layer was covalently attached onto the poly(ethersulfone support layer to improve the membrane electrochemical properties. Followed by amination, a two-layer anion-exchange membrane was prepared. The effect of surface layer treatment using the extraction in various solvents on membrane morphological and electrochemical characteristics was studied. The membranes were tested from the point of view of water content, ion-exchange capacity, specific resistance, permselectivity, FT-IR spectroscopy, and SEM analysis. It was found that the two-layer anion-exchange membranes after the extraction using tetrahydrofuran or toluene exhibited smooth and porous surface layer, which resulted in improved ion-exchange capacity, electrical resistance, and permselectivity of the membranes.

  8. 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.

  9. Nuclear magnetic resonance study on rotational dynamics of water and benzene in a series of ionic liquids: Anion and cation effects.

    OpenAIRE

    Kimura, Hiroshi; Yasaka, Yoshiro; Nakahara, Masaru; Matubayasi, Nobuyuki

    2012-01-01

    The rotational correlation times (τ(2R)) for polar water (D(2)O) molecule and apolar benzene (C(6)D(6)) molecule were determined in ionic liquids (ILs) by means of the (2)H (D) NMR spin-lattice relaxation time (T(1)) measurements. The solvent IL was systematically varied to elucidate the anion and cation effects separately. Five species, bis(trifluoromethylsulfonyl)imide (TFSI(-)), trifluoromethylsulfonate (TfO(-)), hexafluorophosphate (PF(6) (-)), chloride (Cl(-)), and formate (HCOO(-)), wer...

  10. Graphene-coated polymeric anion exchangers for ion chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Kai; Cao, Minyi; Lou, Chaoyan [Department of Chemistry, Xixi Campus, Zhejiang University, Hangzhou 310028 (China); Wu, Shuchao, E-mail: wushch2002@163.com [Zhejiang Institute of Geology and Mineral Resources, Hangzhou 310007 (China); Zhang, Peimin [Department of Chemistry, Xixi Campus, Zhejiang University, Hangzhou 310028 (China); Zhi, Mingyu [Hangzhou Vocational & Technical College, Hangzhou, 310018 (China); Zhu, Yan, E-mail: zhuyan@zju.edu.cn [Department of Chemistry, Xixi Campus, Zhejiang University, Hangzhou 310028 (China)

    2017-06-01

    Carbonaceous stationary phases have gained much attention for their peculiar selectivity and robustness. Herein we report the fabrication and application of a graphene-coated polymeric stationary phase for anion exchange chromatography. The graphene-coated particles were fabricated by a facile evaporation-reduction method. These hydrophilic particles were proven appropriate substrates for grafting of hyperbranched condensation polymers (HBCPs) to make pellicular anion exchangers. The new phase was characterized by zeta potentials, Fourier transform infrared spectroscopy, thermogravimetry and scanning electron microscope. Frontal displacement chromatography showed that the capacities of the anion exchangers were tuned by both graphene amount and HBCPs layer count. The chromatographic performance of graphene-coated anion exchangers was demonstrated with separation of inorganic anions, organic acids, carbohydrates and amino acids. Good reproducibility was obtained by consecutive injections, indicating high chemical stability of the coating. - Highlights: • Graphene-coated polymeric particles were fabricated by a facile method. • Hyperbranched condensation polymers (HBCPs) were grafted from graphene-coated particles to make anion exchangers. • Graphene amount and HBCPs layer count had significant effects on the anion exchange capacities. • Separation of diverse anionic analytes on the anion exchangers was demonstrated. • The prepared anion exchangers exhibited high stability.

  11. Concurrent high-sensitivity conductometric detection of volatile weak acids in a suppressed anion chromatography system.

    Science.gov (United States)

    Liao, Hongzhu; Kadjo, Akinde Florence; Dasgupta, Purnendu K

    2015-08-18

    A suppressed hydroxide eluent anion chromatograph effluent flows through the outside of a gas-permeable membrane tube while electrogenerated 100-200 μM LiOH flows through the lumen into a second conductivity detector. Undissociated volatile acid eluites (e.g., H2S, HCN, H2CO3, etc., represented as HA) transfer through the membrane and react as OH(-) + HA → A(-) + H2O; the conversion of high-mobility OH(-) to lower mobility A(-) results in a significant negative response for these analytes. With the chromatograph operated at a macroscale (0.3 mL/min) the LiOH flow can be 3-30-fold lower, resulting in corresponding enrichment of the transferred analyte prior to detection. Because there is no mixing of liquids, the detector noise is very low (detector. Thus, despite a background of 25-45 μS/cm, limits of detection for sulfide and cyanide are in the submicromolar level, with a linear dynamic range up to 100 μM. Carbonate/bicarbonate can also be sensitively detected. We demonstrate adaptation in a standard commercial system. We also show that Microsoft Excel-based numerical simulations of transport quantitatively predict the observed behavior well.

  12. Cluster-Continuum Calculations of Hydration Free Energies of Anions and Group 12 Divalent Cations

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Hao-Bo [ORNL; Liang, Liyuan [ORNL; Parks, Jerry M [ORNL; Smith, Jeremy C [ORNL; Riccardi, Demian M [ORNL; Gu, Baohua [ORNL

    2013-01-01

    Understanding aqueous phase processes involving group 12 metal cations is relevant to both environmental and biological sciences. Here, quantum chemical methods and polarizable continuum models are used to compute the hydration free energies of a series of divalent group 12 metal cations (Zn2+, Cd2+, and Hg2+) together with Cu2+ and the anions OH , SH , Cl , and F . A cluster-continuum method is employed, in which gas-phase clusters of the ion and explicit solvent molecules are immersed in a dielectric continuum. Two approaches to define the size of the solute-water cluster are compared, in which the number of explicit waters used is either held constant or determined variationally as that of the most favorable hydration free energy. Results obtained with various polarizable continuum models are also presented. Each leg of the relevant thermodynamic cycle is analyzed in detail to determine how different contributions yield the observed mean signed error (MSE) and the standard deviation of the error (STDEV) between theory and experiment. The use of a constant number of water molecules for each set of ions is found to lead to predicted relative trends that benefit from error cancellation. Overall, the best results are obtained with MP2 and the Solvent Model D polarizable continuum model (SMD), with eight explicit water molecules for anions and ten for the metal cations, yielding a STDEV of 2.3 kcal/mol and MSE of 0.9 kcal/mol between theoretical to experimental hydration free energies, which range from -72.4 kcal/mol for SH to -505.9 kcal/mol for Cu2+. Using B3PW91 with DFT-D3 dispersion corrections (B3PW91-D) and SMD yields a STDEV of 3.3 kcal mol 1 and MSE of 1.6 kcal/mol, to which adding MP2 corrections from smaller divalent metal ion water molecule clusters yields very good agreement with the full MP2 results. Using B3PW91-D and SMD, with two explicit water molecules for anions and six for divalent metal cations also yields reasonable agreement with experiment

  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. Gas-Phase Reactivity of Microsolvated Anions

    DEFF Research Database (Denmark)

    Thomsen, Ditte Linde

    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...... for the microsolvated α-nucleophile, and a significant α-effect was observed in this channel. Quantum chemical calculations reveal that the structure of the microsolvated hydrogen peroxide adduct is distinctly different from the structure of the microsolvated alkoxy nucleophiles, in that it involves transfer a proton...... cannot be expected to catalyze hydrogen abstraction reactions by the hydroxyl radical under atmospherically relevant conditions....

  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. Advanced integrated solvent extraction systems

    Energy Technology Data Exchange (ETDEWEB)

    Horwitz, E.P.; Dietz, M.L.; Leonard, R.A. [Argonne National Lab., IL (United States)

    1997-10-01

    Advanced integrated solvent extraction systems are a series of novel solvent extraction (SX) processes that will remove and recover all of the major radioisotopes from acidic-dissolved sludge or other acidic high-level wastes. The major focus of this effort during the last 2 years has been the development of a combined cesium-strontium extraction/recovery process, the Combined CSEX-SREX Process. The Combined CSEX-SREX Process relies on a mixture of a strontium-selective macrocyclic polyether and a novel cesium-selective extractant based on dibenzo 18-crown-6. The process offers several potential advantages over possible alternatives in a chemical processing scheme for high-level waste treatment. First, if the process is applied as the first step in chemical pretreatment, the radiation level for all subsequent processing steps (e.g., transuranic extraction/recovery, or TRUEX) will be significantly reduced. Thus, less costly shielding would be required. The second advantage of the Combined CSEX-SREX Process is that the recovered Cs-Sr fraction is non-transuranic, and therefore will decay to low-level waste after only a few hundred years. Finally, combining individual processes into a single process will reduce the amount of equipment required to pretreat the waste and therefore reduce the size and cost of the waste processing facility. In an ongoing collaboration with Lockheed Martin Idaho Technology Company (LMITCO), the authors have successfully tested various segments of the Advanced Integrated Solvent Extraction Systems. Eichrom Industries, Inc. (Darien, IL) synthesizes and markets the Sr extractant and can supply the Cs extractant on a limited basis. Plans are under way to perform a test of the Combined CSEX-SREX Process with real waste at LMITCO in the near future.

  17. Human-induced changes in landscape configuration influence individual movement routines: lessons from a versatile, highly mobile species.

    Directory of Open Access Journals (Sweden)

    Carlos Camacho

    Full Text Available Landscape conversion by humans may have detrimental effects on animal populations inhabiting managed ecosystems, but human-altered areas may also provide suitable environments for tolerant species. We investigated the spatial ecology of a highly mobile nocturnal avian species-the red-necked nightjar (Caprimulgus ruficollis-in two contrastingly managed areas in Southwestern Spain to provide management recommendations for species having multiple habitat requirements. Based on habitat use by radiotagged nightjars, we created maps of functional heterogeneity in both areas so that the movements of breeding individuals could be modeled using least-cost path analyses. In both the natural and the managed area, nightjars used remnants of native shrublands as nesting sites, while pinewood patches (either newly planted or natural mature and roads were selected as roosting and foraging habitats, respectively. Although the fraction of functional habitat was held relatively constant (60.9% vs. 74.1% in the natural and the managed area, respectively, landscape configuration changed noticeably. As a result, least-cost routes (summed linear distances from nest locations to the nearest roost and foraging sites were three times larger in the natural than in the managed area (mean ± SE: 1356±76 m vs. 439±32 m. It seems likely that the increased proximity of functional habitats in the managed area relative to the natural one is underlying the significantly higher abundances of nightjars observed therein, where breeders should travel shorter distances to link together essential resources, thus likely reducing their energy expenditure and mortality risks. Our results suggest that landscape configuration, but not habitat availability, is responsible for the observed differences between the natural and the managed area in the abundance and movements of breeding nightjars, although no effect on body condition was detected. Agricultural landscapes could be moderately

  18. Proinflammatory effect of high-mobility group protein B1 on keratinocytes: an autocrine mechanism underlying psoriasis development.

    Science.gov (United States)

    Zhang, Weigang; Guo, Sen; Li, Bing; Liu, Lin; Ge, Rui; Cao, Tianyu; Wang, Huina; Gao, Tianwen; Wang, Gang; Li, Chunying

    2017-02-01

    Psoriasis is an autoimmune skin disease, in which keratinocytes play a crucial pathogenic role. High-mobility group protein B1 (HMGB1) is an inflammatory factor that can be released from keratinocyte nuclei in psoriatic lesions. We aimed to investigate the proinflammatory effect of HMGB1 on keratinocytes and the contribution of HMGB1 to psoriasis development. Normal human keratinocytes were treated with recombinant human HMGB1, and the production of inflammatory factors and the intermediary signalling pathways were examined. Furthermore, the imiquimod-induced psoriasis-like mouse model was used to investigate the role of HMGB1 in psoriasis development in vivo. A total of 11 inflammatory factors were shown to be upregulated by HMGB1 in keratinocytes, among which interleukin (IL)-18 showed the greatest change. We then found that activation of the nuclear factor-κB signalling pathway and inflammasomes accounted for HMGB1-induced IL-18 expression and secretion. Moreover, HMGB1 and downstream IL-18 contributed to the development of psoriasiform dermatitis in the imiquimod-treated mice. In addition, T-helper 17 immune response in the psoriasis-like mouse model could be inhibited by both HMGB1 and IL-18 blockade. Our findings indicate that HMGB1 secreted from keratinocytes can facilitate the production and secretion of inflammatory factors such as IL-18 in keratinocytes in an autocrine way, thus promoting the development of psoriasis. Blocking the proinflammatory function of the HMGB1-IL-18 axis may be useful for psoriasis treatment in the future. Copyright © 2016 Pathological Society of Great Britain and Ireland. Published by John Wiley & Sons, Ltd. Copyright © 2016 Pathological Society of Great Britain and Ireland. Published by John Wiley & Sons, Ltd.

  19. Furan Substituted Diketopyrrolopyrrole and Thienylenevinylene Based Low Band Gap Copolymer for High Mobility Organic Thin Film Transistors

    Energy Technology Data Exchange (ETDEWEB)

    Sonar, Prashant [Institute of Materials Research and Engineering (IMRE), Agency for Science, Technology, and Research; Zhuo, Jing-Mei [National University of Singapore (NUS); Zhao, Li-Hong [National University of Singapore; Lim, Kai-Ming [National University of Singapore (NUS); Chen, Jihua [ORNL; Rondinone, Adam Justin [ORNL; Singh, Samarendra [Institute of Materials Research and Engineering (IMRE), Agency for Science, Technology, and Research; Chua, Lay-Lay [National University of Singapore; Ho, Peter [National University of Singapore; Dodabalapur, Ananth [National University of Singapore

    2012-01-01

    A novel solution processable donor-acceptor (D-A) based low band gap polymer semiconductor poly{l_brace}3,6-difuran-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]pyrrole-1,4-dione-alt-thienylenevinylene{r_brace} (PDPPF-TVT), was designed and synthesized by a Pd-catalyzed Stille coupling route. An electron deficient furan based diketopyrrolopyrrole (DPP) block and electron rich thienylenevinylene (TVT) donor moiety were attached alternately in the polymer backbone. The polymer exhibited good solubility, film forming ability and thermal stability. The polymer exhibits wide absorption bands from 400 nm to 950 nm (UV-vis-NIR region) with absorption maximum centered at 782 nm in thin film. The optical band gap (E{sub g}{sup opt}) calculated from the polymer film absorption onset is around 1.37 eV. The {pi}-energy band level (ionization potential) calculated by photoelectron spectroscopy in air (PESA) for PDPPF-TVT is around 5.22 eV. AFM and TEM analyses of the polymer reveal nodular terrace morphology with optimized crystallinity after 200 C thermal annealing. This polymer exhibits p-channel charge transport characteristics when used as the active semiconductor in organic thin-film transistor (OTFT) devices. The highest hole mobility of 0.13 cm{sup 2} V{sup -1} s{sup -1} is achieved in bottom gate and top-contact OTFT devices with on/off ratios in the range of 10{sup 6}-10{sup 7}. This work reveals that the replacement of thiophene by furan in DPP copolymers exhibits such a high mobility, which makes DPP furan a promising block for making a wide range of promising polymer semiconductors for broad applications in organic electronics.

  20. HMGA2, the architectural transcription factor high mobility group, is expressed in the developing and mature mouse cochlea.

    Directory of Open Access Journals (Sweden)

    Ibtihel Smeti

    Full Text Available Hmga2 protein belongs to the non-histone chromosomal high-mobility group (HMG protein family. HMG proteins have been shown to function as architectural transcription regulators, facilitating enhanceosome formation on a variety of mammalian promoters. Hmga2 are expressed at high levels in embryonic and transformed cells. Terminally differentiated cells, however, have been reported to express only minimal, if any, Hmga2. Our previous affymetrix array data showed that Hmga2 is expressed in the developing and adult mammalian cochleas. However, the spatio-temporal expression pattern of Hmga2 in the murine cochlea remained unknown. In this study, we report the expression of Hmga2 in developing and adult cochleas using immunohistochemistry and quantitative real time PCR analysis. Immunolabeling of Hmga2 in the embryonic, postnatal, and mature cochleas showed broad Hmga2 expression in embryonic cochlea (E14.5 at the level of the developing organ of Corti in differentiating hair cells, supporting cells, in addition to immature cells in the GER and LER areas. By postnatal stage (P0-P3, Hmga2 is predominantly expressed in the hair and supporting cells, in addition to cells in the LER area. By P12, Hmga2 immunolabeling is confined to the hair cells and supporting cells. In the adult ear, Hmga2 expression is maintained in the hair and supporting cell subtypes (i.e. Deiters' cells, Hensen cells, pillar cells, inner phalangeal and border cells in the cochlear epithelium. Using quantitative real time PCR, we found a decrease in transcript level for Hmga2 comparable to other known inner ear developmental genes (Sox2, Atoh1, Jagged1 and Hes5 in the cochlear epithelium of the adult relative to postnatal ears. These data provide for the first time the tissue-specific expression and transcription level of Hmga2 during inner ear development and suggest its potential dual role in early differentiation and maintenance of both hair and supporting cell phenotypes.

  1. Urinary levels of high mobility group box-1 are associated with disease activity in antineutrophil cytoplasmic autoantibody-associated vasculitis.

    Directory of Open Access Journals (Sweden)

    Tian-Tian Ma

    Full Text Available High mobility group box-1 (HMGB1, a kind of pro-inflammatory mediator, is associated with inflammatory conditions and tissue damage. Our previous study demonstrated that the circulating levels of HMGB1 correlated with disease activity of antineutrophil cytoplasmic antibody (ANCA-associated vasculitis (AAV. In the current study, we aimed to measure urinary levels of HMGB1 in AAV patients, correlated them to clinical activity index and analysed the immunohistochemical HMGB1 staining in kidney specimens.50 patients with AAV in active stage and 56 patients with AAV in remission were recruited. The urinary levels of HMGB1 were determined by enzyme-linked immunosorbent assay. Moreover, renal biopsy specimens from 27 patients with active AAV were randomly collected to evaluate the deposition of HMGB1.Urinary HMGB1 levels in AAV patients in active stage were significantly higher than those in AAV patients in remission and healthy controls (1.46 [0.56-3.43] versus 0.38 [0.10-1.35] mg/μmolCr, P=0.001; 1.46 [0.56-3.43] versus 0.48 [0.40-0.60] mg/μmolCr, P=0.000, respectively. Further analysis found that urinary levels of HMGB1 correlated with erythrocyte sedimentation rate (r=0.354, p=0.012, C-reactive protein (r=0.289, p=0.042, and Birmingham Vasculitis Activity Score (r=0.350, p=0.013. Renal tissue of active AAV patients showed HMGB1 was mainly expressed in the cytoplasm and the extracellular space. The percentage of HMGB1-negative nuclei in renal tissue of patients with active AAV was significantly higher than that in normal controls (60.6±20.2 % versus 2.7±0.6 %, p<0.01.Urinary levels of HMGB1 may be associated with the disease activity in AAV patients.

  2. Can Static Habitat Protection Encompass Critical Areas for Highly Mobile Marine Top Predators? Insights from Coastal East Africa.

    Directory of Open Access Journals (Sweden)

    Sergi Pérez-Jorge

    Full Text Available Along the East African coast, marine top predators are facing an increasing number of anthropogenic threats which requires the implementation of effective and urgent conservation measures to protect essential habitats. Understanding the role that habitat features play on the marine top predator' distribution and abundance is a crucial step to evaluate the suitability of an existing Marine Protected Area (MPA, originally designated for the protection of coral reefs. We developed species distribution models (SDM on the IUCN data deficient Indo-Pacific bottlenose dolphin (Tursiops aduncus in southern Kenya. We followed a comprehensive ecological modelling approach to study the environmental factors influencing the occurrence and abundance of dolphins while developing SDMs. Through the combination of ensemble prediction maps, we defined recurrent, occasional and unfavourable habitats for the species. Our results showed the influence of dynamic and static predictors on the dolphins' spatial ecology: dolphins may select shallow areas (5-30 m, close to the reefs (< 500 m and oceanic fronts (< 10 km and adjacent to the 100 m isobath (< 5 km. We also predicted a significantly higher occurrence and abundance of dolphins within the MPA. Recurrent and occasional habitats were identified on large percentages on the existing MPA (47% and 57% using presence-absence and abundance models respectively. However, the MPA does not adequately encompass all occasional and recurrent areas and within this context, we propose to extend the MPA to incorporate all of them which are likely key habitats for the highly mobile species. The results from this study provide two key conservation and management tools: (i an integrative habitat modelling approach to predict key marine habitats, and (ii the first study evaluating the effectiveness of an existing MPA for marine mammals in the Western Indian Ocean.

  3. Role of high mobility group box-1 and protection of growth hormone and somatostatin in severe acute pancreatitis

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Y.F. [Department of Surgery, Huashan Hospital, Fudan University, Shanghai (China); Wu, M. [Department of Surgery, Jinshan Pavilion Forest Hospital, Shanghai (China); Ma, B.J.; Cai, D.A.; Yin, B.B. [Department of Surgery, Huashan Hospital, Fudan University, Shanghai (China)

    2014-09-12

    In this study, we investigated the potential role of high-mobility group box 1 (HMGB1) in severe acute pancreatitis (SAP) and the effects of growth hormone (G) and somatostatin (S) in SAP rats. The rats were randomly divided into 6 groups of 20 each: sham-operated, SAP, SAP+saline, SAP+G, SAP+S and SAP+G+S. Ileum and pancreas tissues of rats in each group were evaluated histologically. HMGB1 mRNA expression was measured by reverse transcription-PCR. Levels of circulating TNF-α, IL-1, IL-6, and endotoxin were also measured. In the SAP group, interstitial congestion and edema, inflammatory cell infiltration, and interstitial hemorrhage occurred in ileum and pancreas tissues. The levels of HMGB1, TNF-α, IL-1, IL-6 and endotoxin were significantly up-regulated in the SAP group compared with those in the sham-operated group, and the 7-day survival rate was 0%. In the SAP+G and SAP+S groups, the inflammatory response of the morphological structures was alleviated, the levels of HMGB1, TNF-α, IL-1, IL-6, and endotoxin were significantly decreased compared with those in the SAP group, and the survival rate was increased. Moreover, in the SAP+G+S group, all histological scores were significantly improved and the survival rate was significantly higher compared with the SAP group. In conclusion, HMGB1 might participate in pancreas and ileum injury in SAP. Growth hormone and somatostatin might play a therapeutic role in the inflammatory response of SAP.

  4. Mitochondrial Translocation of High Mobility Group Box 1 Facilitates LIM Kinase 2-Mediated Programmed Necrotic Neuronal Death

    Science.gov (United States)

    Hyun, Hye-Won; Ko, Ah-Reum; Kang, Tae-Cheon

    2016-01-01

    High mobility group box 1 (HMGB1) acts a signaling molecule regulating a wide range of inflammatory responses in extracellular space. HMGB1 also stabilizes nucleosomal structure and facilitates gene transcription. Under pathophysiological conditions, nuclear HMGB1 is immediately transported to the cytoplasm through chromosome region maintenance 1 (CRM1). Recently, we have reported that up-regulation of LIM kinase 2 (LIMK2) expression induces HMGB1 export from neuronal nuclei during status epilepticus (SE)-induced programmed neuronal necrosis in the rat hippocampus. Thus, we investigated whether HMGB1 involves LIMK2-mediated programmed neuronal necrosis, but such role is not reported. In the present study, SE was induced by pilocarpine in rats that were intracerebroventricularly infused with saline, control siRNA, LIMK2 siRNA or leptomycin B (LMB, a CRM1 inhibitor) prior to SE induction. Thereafter, we performed Fluoro-Jade B staining, western blots and immunohistochemical studies. LIMK2 knockdown effectively attenuated SE-induced neuronal death and HMGB1 import into mitochondria accompanied by inhibiting nuclear HMGB1 release and abnormal mitochondrial elongation. LMB alleviated SE-induced neuronal death and nuclear HMGB1 release. However, LMB did not prevent mitochondrial elongation induced by SE, but inhibited the HMGB1 import into mitochondria. The efficacy of LMB was less effective to attenuate SE-induced neuronal death than that of LIMK2 siRNA. These findings indicate that nuclear HMGB1 release and the subsequent mitochondrial import may facilitate and deteriorate programmed necrotic neuronal deaths. The present data suggest that the nuclear HMGB1 release via CRM1 may be a potential therapeutic target for the programmed necrotic neuronal death induced by SE. PMID:27147971

  5. Extracellular high-mobility group box 1 mediates pressure overload-induced cardiac hypertrophy and heart failure.

    Science.gov (United States)

    Zhang, Lei; Liu, Ming; Jiang, Hong; Yu, Ying; Yu, Peng; Tong, Rui; Wu, Jian; Zhang, Shuning; Yao, Kang; Zou, Yunzeng; Ge, Junbo

    2016-03-01

    Inflammation plays a key role in pressure overload-induced cardiac hypertrophy and heart failure, but the mechanisms have not been fully elucidated. High-mobility group box 1 (HMGB1), which is increased in myocardium under pressure overload, may be involved in pressure overload-induced cardiac injury. The objectives of this study are to determine the role of HMGB1 in cardiac hypertrophy and cardiac dysfunction under pressure overload. Pressure overload was imposed on the heart of male wild-type mice by transverse aortic constriction (TAC), while recombinant HMGB1, HMGB1 box A (a competitive antagonist of HMGB1) or PBS was injected into the LV wall. Moreover, cardiac myocytes were cultured and given sustained mechanical stress. Transthoracic echocardiography was performed after the operation and sections for histological analyses were generated from paraffin-embedded hearts. Relevant proteins and genes were detected. Cardiac HMGB1 expression was increased after TAC, which was accompanied by its translocation from nucleus to both cytoplasm and intercellular space. Exogenous HMGB1 aggravated TAC-induced cardiac hypertrophy and cardiac dysfunction, as demonstrated by echocardiographic analyses, histological analyses and foetal cardiac genes detection. Nevertheless, the aforementioned pathological change induced by TAC could partially be reversed by HMGB1 inhibition. Consistent with the in vivo observations, mechanical stress evoked the release and synthesis of HMGB1 in cultured cardiac myocytes. This study indicates that the activated and up-regulated HMGB1 in myocardium, which might partially be derived from cardiac myocytes under pressure overload, may be of crucial importance in pressure overload-induced cardiac hypertrophy and cardiac dysfunction. © 2015 The Authors. Journal of Cellular and Molecular Medicine published by John Wiley & Sons Ltd and Foundation for Cellular and Molecular Medicine.

  6. Scolopendra subspinipes mutilans protected the cerulein-induced acute pancreatitis by inhibiting high-mobility group box protein-1.

    Science.gov (United States)

    Jo, Il-Joo; Bae, Gi-Sang; Park, Kyoung-Chel; Choi, Sun Bok; Jung, Won-Seok; Jung, Su-Young; Cho, Jung-Hee; Choi, Mee-Ok; Song, Ho-Joon; Park, Sung-Joo

    2013-03-14

    To evaluate the inhibitory effects of Scolopendra subspinipes mutilans (SSM) on cerulein-induced acute pancreatitis (AP) in a mouse model. SSM water extract (0.1, 0.5, or 1 g/kg) was administrated intraperitoneally 1 h prior to the first injection of cerulein. Once AP developed, the stable cholecystokinin analogue, cerulein was injected hourly, over a 6 h period. Blood samples were taken 6 h later to determine serum amylase, lipase, and cytokine levels. The pancreas and lungs were rapidly removed for morphological examination, myeloperoxidase assay, and real-time reverse transcription polymerase chain reaction. To specify the role of SSM in pancreatitis, the pancreatic acinar cells were isolated using collagenase method. Then the cells were pre-treated with SSM, then stimulated with cerulein. The cell viability, cytokine productions and high-mobility group box protein-1 (HMGB-1) were measured. Furthermore, the regulating mechanisms of SSM action were evaluated. The administration of SSM significantly attenuated the severity of pancreatitis and pancreatitis associated lung injury, as was shown by the reduction in pancreatic edema, neutrophil infiltration, vacuolization and necrosis. SSM treatment also reduced pancreatic weight/body weight ratio, serum amylase, lipase and cytokine levels, and mRNA expression of multiple inflammatory mediators such as tumor necrosis factor-α and interleukin-1β. In addition, treatment with SSM inhibited HMGB-1 expression in the pancreas during AP. In accordance with in vivo data, SSM inhibited the cerulein-induced acinar cell death, cytokine, and HMGB-1 release. SSM also inhibited the activation of c-Jun NH2-terminal kinase, p38 and nuclear factor (NF)-κB. These results suggest that SSM plays a protective role during the development of AP and pancreatitis associated lung injury via deactivating c-Jun NH2-terminal kinase, p38 and NF-κB.

  7. Genome-wide analyses suggest parallel selection for universal traits may eclipse local environmental selection in a highly mobile carnivore.

    Science.gov (United States)

    Stronen, Astrid Vik; Jędrzejewska, Bogumiła; Pertoldi, Cino; Demontis, Ditte; Randi, Ettore; Niedziałkowska, Magdalena; Borowik, Tomasz; Sidorovich, Vadim E; Kusak, Josip; Kojola, Ilpo; Karamanlidis, Alexandros A; Ozolins, Janis; Dumenko, Vitalii; Czarnomska, Sylwia D

    2015-10-01

    Ecological and environmental heterogeneity can produce genetic differentiation in highly mobile species. Accordingly, local adaptation may be expected across comparatively short distances in the presence of marked environmental gradients. Within the European continent, wolves (Canis lupus) exhibit distinct north-south population differentiation. We investigated more than 67-K single nucleotide polymorphism (SNP) loci for signatures of local adaptation in 59 unrelated wolves from four previously identified population clusters (northcentral Europe n = 32, Carpathian Mountains n = 7, Dinaric-Balkan n = 9, Ukrainian Steppe n = 11). Our analyses combined identification of outlier loci with findings from genome-wide association study of individual genomic profiles and 12 environmental variables. We identified 353 candidate SNP loci. We examined the SNP position and neighboring megabase (1 Mb, one million bases) regions in the dog (C. lupus familiaris) genome for genes potentially under selection, including homologue genes in other vertebrates. These regions included functional genes for, for example, temperature regulation that may indicate local adaptation and genes controlling for functions universally important for wolves, including olfaction, hearing, vision, and cognitive functions. We also observed strong outliers not associated with any of the investigated variables, which could suggest selective pressures associated with other unmeasured environmental variables and/or demographic factors. These patterns are further supported by the examination of spatial distributions of the SNPs associated with universally important traits, which typically show marked differences in allele frequencies among population clusters. Accordingly, parallel selection for features important to all wolves may eclipse local environmental selection and implies long-term separation among population clusters.

  8. Effects of high-mobility group box 1 on the proliferation and odontoblastic differentiation of human dental pulp cells.

    Science.gov (United States)

    Qi, S C; Cui, C; Yan, Y H; Sun, G H; Zhu, S R

    2013-12-01

    To investigate the expression of high-mobility group box 1 (HMGB1) in human dental pulp tissues and the effects of HMGB1 on proliferation and odontoblastic differentiation of human dental pulp cells (hDPCs). Immunohistochemical assay, immunofluorescence staining and flow cytometric analysis were used to detect the expression of HMGB1 in the human dental pulp and hDPCs, respectively. The proliferation of hDPCs was examined by CCK-8 after culturing human primary hDPCs in the presence of HMGB1 with different doses. Odontoblastic differentiation of hDPCs was determined using alkaline phosphatase (ALPase) activity assay and mineralized nodule formation. Important mineralization-related genes such as ALP, dental sialophosphoprotein (DSPP) and dental matrix protein-1 (DMP-1) were determined by real-time polymerase chain reaction. Western blot analysis was performed to determine the difference in expressions of DMP-1 and DSP with or without the presence of exogenous HMGB1. Simultaneously, messenger RNA and protein levels of HMGB1 and RAGE were also detected. The protein level of HMGB1 in the supernatants was quantified using ELISA analysis. HMGB1 was found in human dental pulp tissue and in the nuclei of hDPCs. During hDPC odontoblastic differentiation, HMGB1 translocated from the nuclei to the cytoplasm and then secreted out from hDPCs. Exogenous HMGB1 promoted hDPC proliferation and mineralized nodule formation. It up-regulated the activity of ALPase and the mRNA and protein levels of dentine matrix protein-1 (DMP-1), alkaline phosphatase (ALP), dentine sialophosphoprotein (DSPP) and receptor for advance glycation end (RAGE) of hDPCs. HMGB1 promoted the proliferation and odontoblastic differentiation of hDPCs. © 2013 International Endodontic Journal. Published by John Wiley & Sons Ltd.

  9. Switching the Structural Force in Ionic Liquid-Solvent Mixtures by Varying Composition

    Science.gov (United States)

    Smith, Alexander M.; Lee, Alpha A.; Perkin, Susan

    2017-03-01

    The structure and interactions in electrolytes at high concentration have implications from energy storage to biomolecular interactions. However, many experimental observations are yet to be explained in these mixtures, which are far beyond the regime of validity of mean-field models. Here, we study the structural forces in a mixture of ionic liquid and solvent that is miscible in all proportions at room temperature. Using the surface force balance to measure the force between macroscopic smooth surfaces across the liquid mixtures, we uncover an abrupt increase in the wavelength above a threshold ion concentration. Below the threshold concentration, the wavelength is determined by the size of the solvent molecule, whereas above the threshold, it is the diameter of a cation-anion pair that determines the wavelength.

  10. Analysis of anions in beer using ion chromatography

    OpenAIRE

    Bruce, Jonathan

    2002-01-01

    The majority of anions found in beer are a consequence of impurities derived from the water used during the brewing process. The process of beer manufacture consists of malting, brewing and fermentation followed by maturation before filtration and finally storage. Strict quality control is required because the presence of certain anions outside strictly defined tolerance limits can affect the flavour characteristics of the finished product. The anions present were quantified using the techniq...

  11. Unexpectedly strong anion-π interactions on the graphene flakes.

    Science.gov (United States)

    Shi, Guosheng; Ding, Yihong; Fang, Haiping

    2012-05-30

    Interactions of anions with simple aromatic compounds have received growing attention due to their relevancy in various fields. Yet, the anion-π interactions are generally very weak, for example, there is no favorable anion-π interaction for the halide anion F(-) on the simplest benzene surface unless the H-atoms are substituted by the highly negatively charged F. In this article, we report a type of particularly strong anion-π interactions by investigating the adsorptions of three halide anions, that is, F(-), Cl(-), and Br(-), on the hydrogenated-graphene flake using the density functional theory. The anion-π interactions on the graphene flake are shown to be unexpectedly strong compared to those on simple aromatic compounds, for example, the F(-)-adsorption energy is as large as 17.5 kcal/mol on a graphene flake (C(84) H(24)) and 23.5 kcal/mol in the periodic boundary condition model calculations on a graphene flake C(113) (the supercell containing a F(-) ion and 113 carbon atoms). The unexpectedly large adsorption energies of the halide anions on the graphene flake are ascribed to the effective donor-acceptor interactions between the halide anions and the graphene flake. These findings on the presence of very strong anion-π interactions between halide ions and the graphene flake, which are disclosed for the first time, are hoped to strengthen scientific understanding of the chemical and physical characteristics of the graphene in an electrolyte solution. These favorable interactions of anions with electron-deficient graphene flakes may be applicable to the design of a new family of neutral anion receptors and detectors. Copyright © 2012 Wiley Periodicals, Inc.

  12. 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.

  13. The quantum structure of anionic hydrogen clusters

    Science.gov (United States)

    Calvo, F.; Yurtsever, E.

    2018-03-01

    A flexible and polarizable interatomic potential has been developed to model hydrogen clusters interacting with one hydrogen anion, (H2)nH-, in a broad range of sizes n = 1-54 and parametrized against coupled cluster quantum chemical calculations. Using path-integral molecular dynamics simulations at 1 K initiated from the putative classical global minima, the equilibrium structures are found to generally rely on icosahedral shells with the hydrogen molecules pointing toward the anion, producing geometric magic numbers at sizes n = 12, 32, and 44 that are in agreement with recent mass spectrometry measurements. The energetic stability of the clusters is also connected with the extent of vibrational delocalization, measured here by the fluctuations among inherent structures hidden in the vibrational wave function. As the clusters grow, the outer molecules become increasingly free to rotate, and strong finite size effects are also found between magic numbers, associated with more prominent vibrational delocalization. The effective icosahedral structure of the 44-molecule cluster is found to originate from quantum nuclear effects as well, the classical structure showing no particular symmetry.

  14. 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.

  15. Fluorescence quenching of etilefrine by acetate anion

    Science.gov (United States)

    Quintero Osso, B.; Carazo Rodríguez, F. M.; Morales Domingo, J. J.; Cabeza González, M. C.; Thomas Gómez, J.

    1999-02-01

    Acid dissociation in the excited state of antihypotensor drug etilefrine [2-(ethylamino1-3-hydroxyphenyl)ethanol] is studied. Fluorescence of etilefrine decreases at pH7. Analyses of the absorption and fluorescence spectra of aqueous solutions of etilefrine in the presence of acetate anions have been made. Considering the existence of an equilibrium in the excited state the values of 3.47×10 -9 and 0.216×10 -9 M -1 s -1 have been obtained for the rate constants for direct and inverse reactions, respectively. Moreover, the lifetime ( τ0'=0.58×10 -9 s) and quantum yield (0.01) of non-protonated etilefrine have been determined. Our results seem to support the existence of a dynamic quenching process based on a proton transfer mechanism induced by acetate anions. This process could represent a serious inconvenience in analytical fluorimetric techniques taking into account that the acetic acid/acetate pair is commonly used as a buffer. Additional fluorescence quenching by H + ions could be involved in acid aqueous mediums. At high concentrations of acetic acid, a value of 2.98×10 -9 M -1 s -1 for the bimolecular constant for the quenching by H + has been calculated.

  16. 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....

  17. Synthesis and characterization of solvent-free ionic molybdenum disulphide (MoS{sub 2}) nanofluids

    Energy Technology Data Exchange (ETDEWEB)

    Gu, Shu-Ying, E-mail: gushuying@tongji.edu.cn [School of Materials Science and Engineering, Tongji University, Shanghai 201804 (China); Key Laboratory of Advanced Civil Engineering Materials, Ministry of Education, School of Materials Science and Engineering, Tongji University, Shanghai 201804 (China); Gao, Xie-Feng; Zhang, Yi-Han [School of Materials Science and Engineering, Tongji University, Shanghai 201804 (China)

    2015-01-15

    A development of the novel and stable solvent-free ionic MoS{sub 2} nanofluids by a facile and scalable hydrothermal method is presented. The nanofluids were synthesized by surface functionalizing nanoscale MoS{sub 2} from hydrothermal synthesis with a charged corona, and ionically tethering with oligomeric chains as a canopy. The structures and properties of the nanofluids were characterized by Fourier transform infrared (FTIR), nuclear magnetic resonance (NMR, {sup 1}H), differential scanning calorimeter (DSC), thermogravimetric analysis (TGA) and ARES rheometer. The obtained solvent-free nanofluids are homogeneous, stable amber-like fluids with no evidence of phase separation. The nanofluids could be easily dispersed in both aqueous and organic solvents to form transparent and stable liquids due to the ionic nature and the presence of oligomeric polymer chains. It was found that the solvent-free nanofluids with up to 32 wt% inorganic content show Newtonian rheological behaviors due to the high graft density and uniform dispersion of inorganic cores, indicating that the nanofluids would have a stable lubricating performance. As reported in our previous communication, the nanofluids showing lower, more stable friction coefficients of less than 0.1 with self-healing lubricating behaviors. For deeper understanding of the nanofluids, the details of synthesis, chemical structures, rheological behaviors and molecular dynamics of the nanofluids were investigated in details. The rheological behaviors can be tailored by varying the grafting density of the canopy. Dynamic results of the canopy of the MoS{sub 2} nanofluids show that inorganic MoS{sub 2} cores have hindrance effect on the canopy segmental motions above 253 K due to their effect to the mobility of anions and the departing-recombining motions between the paired cations and anions. - Highlights: • A development of the novel synthesis of solvent-free MoS{sub 2} nanofluids is presented. • The rheological

  18. Positron Spur Reactions with Excess Electrons and Anions in Liquid Organic Mixtures of Electron Acceptors

    DEFF Research Database (Denmark)

    Lévay, B.; Mogensen, O. E.

    1980-01-01

    By means of the positron lifetime technique we have measured positronium (Ps) yields in mixtures of nonpolar liquids with various electron scavengers which bind the electron fairly weakly (1–2 eV) in stable anions. The results are discussed with reference to recent excess electron works, and new...... curve. Alcohol clusters did not show antiinhibition in 0.05 M CCl4/neopentane system. Weak electron scavengers (C6F6, naphthalene, biphenyl, benzene) which generally act as antiinhibitors were added to pure non-polar solvents (hexane, isooctane, cyclohexane) and caused Ps enhancement. This can...... to the system, indicating that antirecombination and antiinhibition took place simultaneously. On addition of hexane, isooctane, CS2 or 0.8 M CS2/hexane to pure C6F6 the Ps yield drastically decreased. This correlates well with the drastic decrease of the electron mobility by adding similar additives to C6F6...

  19. Sodium polyacrylate adsorption onto anionic and cationic silica in the presence of salts.

    Science.gov (United States)

    Flood, Charlie; Cosgrove, Terence; Espidel, Youssef; Howell, Ian; Revell, Patricia

    2007-05-22

    Sodium polyacrylate is well known for its application as a scale inhibitor in common household products, and the effects of both monovalent and divalent metal cations on its structure have been covered by a range of previous publications. In the present article, we extend this work by using solvent relaxation NMR to look at the adsorption of the polyelectrolyte onto both positively and negatively charged silica and how this is altered by calcium chloride. In the anionic case, we found that polyacrylate adsorption was predictably very weak, and interestingly, perhaps counterintuitively, it was further reduced by calcium ions. This is probably linked to NaPA-Ca2+ binding, which changes the conformation and charge of the polyelectrolyte. In contrast, NaPA adsorbs very strongly on cationic silica, to the point that precipitation often occurs, particularly on addition of salt.

  20. Solvent characterization using the dispersion number

    Energy Technology Data Exchange (ETDEWEB)

    Leonard, R. A.

    1993-10-06

    When developing new solvent extraction processes, one often has to evaluate new solvents, new aqueous phases, or both for their ability to work in plant-scale equipment. To facilitate solvent characterization, a simple test is proposed based on the dimensionless dispersion number (N{sub Di}). It allows one to characterize the ability of the solvent to separate from a two-phase dispersion and allows one to estimate process throughput for equipment of a given size. Several ways to carry out the N{sub Di} test are given, including a standard test procedure. The N{sub Di} test was applied to the performance of solvent extraction equipment with discrete process stages, the leaching of plasticizers from plastic tubing, and the development of a new solvent for the combined extraction of strontium and transuranic elements.

  1. Toxic hepatitis in occupational exposure to solvents

    OpenAIRE

    Malaguarnera, Giulia; Cataudella, Emanuela; Giordano, Maria; Nunnari, Giuseppe; Chisari, Giuseppe; Malaguarnera, Mariano

    2012-01-01

    The liver is the main organ responsible for the metabolism of drugs and toxic chemicals, and so is the primary target organ for many organic solvents. Work activities with hepatotoxins exposures are numerous and, moreover, organic solvents are used in various industrial processes. Organic solvents used in different industrial processes may be associated with hepatotoxicity. Several factors contribute to liver toxicity; among these are: species differences, nutritional condition, genetic facto...

  2. Organic Solvent Effects in Biomass Conversion Reactions

    OpenAIRE

    Shuai, Li; LUTERBACHER, Jeremy

    2016-01-01

    Transforming lignocellulosic biomass into fuels and chemicals has been intensely studied in recent years. A large amount of work has been dedicated to finding suitable solvent systems, which can improve the transformation of biomass into value-added chemicals. These efforts have been undertaken based on numerous research results that have shown that organic solvents can improve both conversion and selectivity of biomass to platform molecules. We present an overview of these organic solvent ef...

  3. Femtosecond dynamics in hydrogen-bonded solvents

    Energy Technology Data Exchange (ETDEWEB)

    Castner, E.W. Jr.; Chang, Y.J.

    1993-09-01

    We present results on the ultrafast dynamics of pure hydrogen-bonding solvents, obtained using femtosecond Fourier-transform optical-heterodyne-detected, Raman-induced Kerr effect spectroscopy. Solvent systems we have studied include the formamides, water, ethylene glycol, and acetic acid. Inertial and diffusive motions are clearly resolved. We comment on the effect that such ultrafast solvent motions have on chemical reactions in solution.

  4. Supercritical solvent extraction of oil sand bitumen

    Science.gov (United States)

    Imanbayev, Ye. I.; Ongarbayev, Ye. K.; Tileuberdi, Ye.; Mansurov, Z. A.; Golovko, A. K.; Rudyk, S.

    2017-08-01

    The supercritical solvent extraction of bitumen from oil sand studied with organic solvents. The experiments were performed in autoclave reactor at temperature above 255 °C and pressure 29 atm with stirring for 6 h. The reaction resulted in the formation of coke products with mineral part of oil sands. The remaining products separated into SARA fractions. The properties of the obtained products were studied. The supercritical solvent extraction significantly upgraded extracted natural bitumen.

  5. Lanthanide-organic complexes based on polyoxometalates: Solvent effect on the luminescence properties

    Science.gov (United States)

    Tang, Qun; Liu, Shu-Xia; Liang, Da-Dong; Ma, Feng-Ji; Ren, Guo-Jian; Wei, Feng; Yang, Yuan; Li, Cong-Cong

    2012-06-01

    A series of lanthanide-organic complexes based on polyoxometalates (POMs) [Ln2(DNBA)4(DMF)8][W6O19] (Ln=La(1), Ce(2), Sm(3), Eu(4), Gd(5); DNBA=3,5-dinitrobenzoate; DMF=N,N-dimethylformamide) has been synthesized. These complexes consist of [W6O19]2- and dimeric [Ln2(DNBA)4(DMF)8]2+ cations. The luminescence properties of 4 are measured in solid state and different solutions, respectively. Notably, the emission intensity increases gradually with the increase of solvent permittivity, and this solvent effect can be directly observed by electrospray mass spectrometry (ESI-MS). The analyses of ESI-MS show that the eight coordinated solvent DMF units of dimeric cation are active. They can move away from dimeric cations and exchange with solvent molecules. Although the POM anions escape from 3D supramolecular network, the dimeric state structure of [Ln2(DNBA)4]2+ remains unchanged in solution. The conservation of red luminescence is attributed to the maintenance of the aggregated state structures of dimeric cations.

  6. Conformational analysis of glutamic acid: a density functional approach using implicit continuum solvent model.

    Science.gov (United States)

    Turan, Başak; Selçuki, Cenk

    2014-09-01

    Amino acids are constituents of proteins and enzymes which take part almost in all metabolic reactions. Glutamic acid, with an ability to form a negatively charged side chain, plays a major role in intra and intermolecular interactions of proteins, peptides, and enzymes. An exhaustive conformational analysis has been performed for all eight possible forms at B3LYP/cc-pVTZ level. All possible neutral, zwitterionic, protonated, and deprotonated forms of glutamic acid structures have been investigated in solution by using polarizable continuum model mimicking water as the solvent. Nine families based on the dihedral angles have been classified for eight glutamic acid forms. The electrostatic effects included in the solvent model usually stabilize the charged forms more. However, the stability of the zwitterionic form has been underestimated due to the lack of hydrogen bonding between the solute and solvent; therefore, it is observed that compact neutral glutamic acid structures are more stable in solution than they are in vacuum. Our calculations have shown that among all eight possible forms, some are not stable in solution and are immediately converted to other more stable forms. Comparison of isoelectronic glutamic acid forms indicated that one of the structures among possible zwitterionic and anionic forms may dominate over the other possible forms. Additional investigations using explicit solvent models are necessary to determine the stability of charged forms of glutamic acid in solution as our results clearly indicate that hydrogen bonding and its type have a major role in the structure and energy of conformers.

  7. Ultrasensitive 4-methylumbelliferone fluorimetric determination of water contents in aprotic solvents.

    Science.gov (United States)

    Kłucińska, Katarzyna; Jurczakowski, Rafał; Maksymiuk, Krzysztof; Michalska, Agata

    2015-01-01

    A novel approach to the quantification of relatively small amounts of water present in low polarity, aprotic solvents is proposed. This method takes advantage of protolitic reaction of 4-methylumbelliferone dissolved in the solvent with water, acting as a base. The low emission intensity neutral 4-methylumbelliferone is transformed in reaction with water to a highly fluorescent anionic form. Thus the increase in emission intensity is observed for increasing water contents in aprotic solvents. For low water contents and highly lipophilic solvents, this method yields (in practical conditions) higher sensitivity compared to biamperometric Karl Fischer titration method in volumetric mode. It is also shown that organic compounds of protolitic character (amines, acids) not only interfere with water contents determination but increase the sensitivity of emission vs. water contents dependence. Introduction of aqueous solution of strong acid or base (HCl or NaOH) has similar effect on the system as introduction of pure water. Copyright © 2014 Elsevier B.V. All rights reserved.

  8. Spectrophotometric Determination of Selenium Through Triiodide Anion.

    Science.gov (United States)

    Bizerea-Spiridon, Otilia; Nartita, Radu; Rogobete, Alexandru F; Negrea, Adina; Stroescu, Ramona; Bizerea, Teofana O; Ilie, Constantin; Marginean, Otilia

    2017-05-01

    Selenium is a chemical element found in the human body that plays a crucial role in its regulation. Depending on the concentration, it may have beneficial or have toxic effects. Selenium is incorporated as selenocysteine amino acid residue in selenoproteins which play an important role in many biological functions: anti-oxidant defense, regulation of the immune function and of the inflammatory response, metabolism of thyroid hormones, functioning of the central nervous system, biosynthesis of DNA and RNA, fertility, and reproduction. Excess selenium, altough less common than selenium deficiency, has equally important negative effects. Given the importance of selenium quantification in various samples, the study proposes a simple and direct spectrophotometric determination of selenium using triiodide anions. The method is based on the oxidation of iodide in acidic medium by selenium (IV) contained in the sample, to form elemental iodine which, in turn, reacts with the excess iodide to form the triiodide anions, the most stable soluble species in aqueous solution. Triiodide is colored from yellow to brown, depending on the concentration. The coloured compound has maximum absorbance at specific wavelengths and thus, the stage of interaction with a chromogenic agent is eliminated. Due to the sensitivity of the reaction, the detection limit of triiodide, and therefore selenium, is extended toward lower values. The optimal conditions for the measurements were established: λ = 290 nm, pH = 1.0 - 1.5, reaction time = 15 minutes. Two areas of selenium detection were determined from the samples: 0.025 - 0.100 ppm, and 0.1 - 4.0 ppm. The detection limit of selenium was lowered at 0.100 ppm and even at 0.025 ppm, which significantly improves the sensitivity of the determination. Types of samples were specified which are suitable for analysis using the proposed method and explained why, in case of biological fluids, it must be used only accompanied by an adequate digestion

  9. Aminosilicone solvent recovery methods and systems

    Energy Technology Data Exchange (ETDEWEB)

    Spiry, Irina Pavlovna; Perry, Robert James; Wood, Benjamin Rue; Singh, Surinder Prabhjot; Farnum, Rachel Lizabeth; Genovese, Sarah Elizabeth

    2018-02-13

    The present invention is directed to aminosilicone solvent recovery methods and systems. The methods and systems disclosed herein may be used to recover aminosilicone solvent from a carbon dioxide containing vapor stream, for example, a vapor stream that leaves an aminosilicone solvent desorber apparatus. The methods and systems of the invention utilize a first condensation process at a temperature from about 80.degree. C. to about 150.degree. C. and a second condensation process at a temperature from about 5.degree. C. to about 75.degree. C. The first condensation process yields recovered aminosilicone solvent. The second condensation process yields water.

  10. [Expression of high mobility group box-1 in the lung tissue and serum of patients with pulmonary tuberculosis].

    Science.gov (United States)

    Yang, Xiao-min; Yang, Hua

    2013-07-01

    To explore the expression of high mobility group box-1 (HMGB1) in the lung tissue and serum of patients with pulmonary tuberculosis and to explore its relationship with tumor necrosis factor (TNF)-α and interleukin(IL)-1β. Sixty samples of lung tissues were obtained from patients with pulmonary tuberculosis who had underwent pneumonectomy in Department of Chest Surgery, First Affiliated Hospital of Zunyi Medical College from June 2010 to December 2011. At the same period, 40 normal lung samples were also obtained from patients with pulmonary contusion and lung cancer by surgical resections as the control group. The mRNA expressions of HMGB1 was detected by reverse transcription-polymerase chain reaction (RT-PCR), and the protein level of HMGB1 was measured by immunohistochemical staining of tissue microarrays in lung tissue. Blood samples were taken from 89 patients with active pulmonary tuberculosis (pulmonary tuberculosis group), including hematogenous disseminated pulmonary tuberculosis (type II) in 35 cases and secondary pulmonary tuberculosis (type III) in 54 cases, and 50 healthy volunteers (control group). Furthermore, the 54 patients with secondary pulmonary tuberculosis were divided into different subgroups according to cavity formation and the lung fields involved: patients without lung cavity (35 cases) vs those with lung cavity (19 cases), patients with involvement of pulmonary tuberculosis (69 ± 29) was significantly higher than that in normal lung tissue (22 ± 12) (t = 2.389, P pulmonary tuberculosis (786 ± 86) was significantly higher than that in normal lung tissue (202 ± 60) (t = 3.872, P pulmonary tuberculosis group were (5.0 ± 3.2) µg/L, (118 ± 77) ng/L and (33 ± 20) ng/L, respectively, which were significantly higher than those in the control group [(1.7 ± 1.0) µg/L, (40 ± 11) ng/L and (18 ± 12) ng/L, respectively], the respective t values being -0.928, 4.268 and 11.064, all P pulmonary tuberculosis, the serum concentration of HMGB

  11. Low-temperature carrier dynamics in high-mobility organic transistors of alkylated dinaphtho-thienothiophene as investigated by electron spin resonance

    Energy Technology Data Exchange (ETDEWEB)

    Kinoshita, Yutaro; Tanaka, Hisaaki, E-mail: htanaka@nuap.nagoya-u.ac.jp; Kuroda, Shin-ichi [Department of Applied Physics, Nagoya University, Chikusa, Nagoya 464-8603 (Japan); Shimoi, Yukihiro [Nanosystem Research Institute (NRI), National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Umezono, Tsukuba, Ibaraki 305-8568 (Japan); Takimiya, Kazuo [Emergent Molecular Function Research Group, RIKEN Center for Emergent Matter Science (CEMS), Wako, Saitama 351-0198 (Japan)

    2014-07-21

    Charge carriers in high-mobility organic thin-film transistors of alkylated dinaphtho-thienothiophene (C{sub 10}-DNTT) have been directly observed by field-induced electron spin resonance (FI-ESR) down to 4 K. FI-ESR spectra of π-electron hole carriers of C{sub 10}-DNTT exhibited clear anisotropy, indicating a highly organized end-on molecular orientation at the device interface. The intra-grain and inter-grain carrier motion were probed by the motional narrowing effect of the ESR spectra. The intra-grain motion was clearly observed even at 4 K, showing intrinsically high mobility of C{sub 10}-DNTT crystallites. On the other hand, significantly low activation energy of ∼10 meV for inter-grain carrier hopping, compared with pristine DNTT, was observed, which shows that the alkyl substitution drastically enhances the carrier mobility of DNTT system.

  12. Radio-iodide uptake by modified poly (glycidyl methacrylate) as anion exchange resin

    Energy Technology Data Exchange (ETDEWEB)

    Othman, Sameh H. [Atomic Energy Authority, Cairo (Egypt). Nuclear Research Center; Atomic Energy Authority, Cairo (Egypt). Second Research Reactor; Elbarbary, Ahmed M. [Atomic Energy Authority, Cairo (Egypt). Radiation Research of Polymer Chemistry Dept.; Rashad, Ghada; Fasih, T.W. [Atomic Energy Authority, Cairo (Egypt). Hot Laboratories Center

    2017-03-01

    Poly(glycidyl methacrylate) (PGMA) microspheres were prepared by radiation induced polymerization of glycidyl methacrylate (GMA) monomer. The factors affecting the degree of polymerization and yield (%) of PGMA such as type of solvent, monomer concentration, and irradiation dose were investigated. It was found that the PGMA yield (%) increases with increasing monomer concentration up to 50% and absorbed dose of 5 kGy. The resulting PGMA containing the epoxy group was chemically modified by hydroxyl amine to act as anion-exchange resin for uptake of {sup 131}I{sup -} ions. The modified PGMA (MPGMA) was characterized by Fourier transform infrared (FT-IR) spectrophotometer, thermal gravimetric analysis (TGA) and scanning electron microscopy (SEM). I-131 is produced from the fission of U-235 with low-enrichment uranium (LEU) targets in the Egyptian Second Research Reactor (ETRR-2). Separation of iodide from the radioactive solution by batchwise and column techniques was employed to determine the adsorption capacity of the MPGMA. Quality control of {sup 131}I product solution and radiochemical purity was examined by using the ascending paper chromatography method. The uptake behavior of MPGMA towards {sup 131}I{sup -} ions were studied at different experimental conditions and achieved by X-ray fluorescence (XRF). The synthesized MPGMA showed good results as anion-exchange and an effective adsorbent for uptaking {sup 131}I{sup -} ions.

  13. Synthesis of stable ligand-free gold-palladium nanoparticles using a simple excess anion method.

    Science.gov (United States)

    Sankar, Meenakshisundaram; He, Qian; Morad, Moataz; Pritchard, James; Freakley, Simon J; Edwards, Jennifer K; Taylor, Stuart H; Morgan, David J; Carley, Albert F; Knight, David W; Kiely, Christopher J; Hutchings, Graham J

    2012-08-28

    We report a convenient excess anion modification and post-reduction step to the impregnation method which permits the reproducible preparation of supported bimetallic AuPd nanoparticles having a tight particle size distribution comparable to that found for sol-immobilization materials but without the complication of ligands adsorbed on the particle surface. The advantageous features of the modified impregnation materials compared to those made by conventional impregnation include a smaller average particle size, an optimized random alloy composition, and improved compositional uniformity from particle-to-particle resulting in higher activity and stability compared to the catalysts prepared using both conventional impregnation and sol immobilization methods. Detailed STEM combined with EDX analyses of individual particles have revealed that an increase in anion concentration increases the gold content of individual particles in the resultant catalyst, thus providing a method to control/tune the composition of the nanoalloy particles. The improved activity and stability characteristics of these new catalysts are demonstrated using (i) the direct synthesis of hydrogen peroxide and (ii) the solvent-free aerobic oxidation of benzyl alcohol as case studies.

  14. Effect of anionic surfactants on grafting density of gelatin modified with PDMS-E.

    Science.gov (United States)

    Xu, Jing; Xu, Zhen; Qiao, Cong-De; Li, Tian-Duo

    2014-02-01

    The effect of anionic surfactants on the interfacial compatibility in mono epoxy terminated polydimethylsiloxane (PDMS-E) macromonomer and gelatin mixed system was studied by Gibbs free energy (ΔGM), which played a crucial role in deciding the grafting density of immiscible polymer in heterogeneous system. Aggregation behavior of gelatin chains at boundary between gelatin phase and solvent phase was investigated using viscosity, surface tension and conductivity measurements. Viscosity analysis showed a regular increase in viscosity with the increasing alkyl chain length from C7 to C16 of the homologous alkyl sulfate surfactants. Changes of surface tension exhibited the regular curves of polyelectrolyte-anionic surfactant for alkyl sulfate surfactant systems. The results demonstrated that aggregate structure of gelatin-sulfate surfactants was dominated by electrostatic and hydrophobic interactions, which resulted in a self-assembly process of the hydrophobic segments and hydrophilic segments among gelatin chains and surfactant molecules. However, the interactions between gelatin and alkyl sulfonate surfactants were mainly governed by hydrophobic interactions, which induced conformation change of gelatin molecules. Well-ordered arrangement of gelatin chains at a fluid interface has observed by high-resolution transmission electron microscopy (HR-TEM). It is a key factor to contribute to the reduction of interfacial free energy, which mainly depends on the hydrophobic interaction between gelatin and alkyl sulfate/sulfonate surfactants. MD simulations conclusions are great agreement with our experimental results. Copyright © 2013 Elsevier B.V. All rights reserved.

  15. Behaviour of fibroblasts on water born acrylonitrile-based copolymers containing different cationic and anionic moieties.

    Science.gov (United States)

    Scharnagl, N; Hiebl, B; Trescher, K; Zierke, M; Behl, M; Kratz, K; Jung, F; Lendlein, A

    2012-01-01

    The chemical composition of a substrate can influence the adhesion, viability and proliferation of cells seeded on the substrate. The aim of this work was to investigate the influence of different cationic or anionic moieties in acrylonitrile-based copolymers on the interaction with fibroblasts. A series of ten different types of acrylonitrile-based copolymers with a random sequence structure was prepared using a water born synthesis process to exclude potential residues of organic solvents. As charged comonomers cationic methacrylic acid-2-aminoethylester hydrochloride (AEMA), N-3-amino-propyl-methacrylamide hydrochloride (APMA) and anionic 2-methyl-2-propene-1-sulfonic acid sodium salt (NaMAS) were utilized. By application of a specific sintering procedure the copolymer materials were processed into transparent disks for conducting cell tests in direct contact. The copolymers were analyzed with respect to their composition and surface properties. Cytotoxicity tests of the polymer extracts, as well as of the disks were performed with L929 mouse fibroblasts. All copolymers showed no cytotoxic effects. Furthermore, for higher molar ratios of AEMA an increase in cell growth could be observed, which might be a hint that higher charge densities are favorable for the proliferation of L929 cells.

  16. Gas Phase Reactions of Ions Derived from Anionic Uranyl Formate and Uranyl Acetate Complexes

    Science.gov (United States)

    Perez, Evan; Hanley, Cassandra; Koehler, Stephen; Pestok, Jordan; Polonsky, Nevo; Van Stipdonk, Michael

    2016-12-01

    The speciation and reactivity of uranium are topics of sustained interest because of their importance to the development of nuclear fuel processing methods, and a more complete understanding of the factors that govern the mobility and fate of the element in the environment. Tandem mass spectrometry can be used to examine the intrinsic reactivity (i.e., free from influence of solvent and other condensed phase effects) of a wide range of metal ion complexes in a species-specific fashion. Here, electrospray ionization, collision-induced dissociation, and gas-phase ion-molecule reactions were used to create and characterize ions derived from precursors composed of uranyl cation (UVIO2 2+) coordinated by formate or acetate ligands. Anionic complexes containing UVIO2 2+ and formate ligands fragment by decarboxylation and elimination of CH2=O, ultimately to produce an oxo-hydride species [UVIO2(O)(H)]-. Cationic species ultimately dissociate to make [UVIO2(OH)]+. Anionic complexes containing acetate ligands exhibit an initial loss of acetyloxyl radical, CH3CO2•, with associated reduction of uranyl to UVO2 +. Subsequent CID steps cause elimination of CO2 and CH4, ultimately to produce [UVO2(O)]-. Loss of CH4 occurs by an intra-complex H+ transfer process that leaves UVO2 + coordinated by acetate and acetate enolate ligands. A subsequent dissociation step causes elimination of CH2=C=O to leave [UVO2(O)]-. Elimination of CH4 is also observed as a result of hydrolysis caused by ion-molecule reaction with H2O. The reactions of other anionic species with gas-phase H2O create hydroxyl products, presumably through the elimination of H2.

  17. Selected anionic and cationic surface active agents: case study on the Kłodnica sediments

    Directory of Open Access Journals (Sweden)

    Olkowska Ewa

    2017-03-01

    Full Text Available Surface active agents (surfactants are a group of chemical compounds, which are used as ingredients of detergents, cleaning products, cosmetics and functional products. After use, wastes containing surfactants or their degradation products are discharged to wastewater treatment plants or directly into surface waters. Due to their specific properties of SAAs, compounds are able to migrate between different environmental compartments such as soil, sediment, water or even living organisms and accumulate there. Surfactants can have a harmful effect on living organisms. They can connect with bioactive molecules and modify their function. Additionally, they have the ability to migrate into cells and cause their damage or death. For these reasons investigation of individual surfactants should be conducted. The presented research has been undertaken to obtain information about SAA contamination of sediment from the River Kłodnica catchment caused by selected anionic (linear alkylbenzene sulfonates (LAS C10-C13 and cationic (alkylbenzyldimethylammonium (BDMA-C12-16, alkyl trimethyl ammonium (DTMA, hexadecyl piridinium chloride (HP chlorides surfactants. This river flows through an area of the Upper Silesia Industrial Region where various companies and other institutions (e.g. coal mining, power plants, metallurgy, hospitals are located. To determine their concentration the following analytical tools have been applied: accelerated solvent extraction– solid phase extraction – high performance liquid chromatography – UV-Vis (anionic SAAs and conductivity (cationic SAAs detectors. In all sediments anionic SAAs have been detected. The concentrations of HTMA and BDMA-C16 in tested samples were higher than other cationic analytes. Generally, levels of surfactants with longer alkyl chains were higher and this observation can confirm their higher susceptibility to sorption on solid surfaces.

  18. Use of anions of C{sub 60} as electrogenerated bases

    Energy Technology Data Exchange (ETDEWEB)

    Niyazymbetov, M.E.; Evans, D.H. [Univ. of Delaware, Newark, DE (United States). Dept. of Chemistry and Biochemistry

    1995-08-01

    C{sub 60} was reduced in the mixed solvent acetonitrile-toluene (2:3) to form a series of three electrogenerated bases of successively increasing basicity. These were the radical anion, the dianion, and the radical trianion of the fullerene. Cyclic voltammograms indicated that the radical anion was capable of deprotonating the relatively strong C-H acid, ethyl nitroacetate. The weaker acid, diethyl malonate, required the stronger base C{sub 60}{sup 2{minus}} in order to observe deprotonation on the voltammetric time scale. Other weak acids that react with C{sub 60}{sup 2{minus}} include diethyl methylalonate, 2-nitropropane, and n-octanethiol. The anionic electrogenerated bases were used to carry out efficient base-catalyzed synthetic reactions. These included the C{sub 60}{sup {minus}{sm_bullet}}-catalyzed reaction of ethyl nitroacetate with ethyl acrylate and acrylonitrile to form double addition products. The dianion promoted reaction of nitromethane with ethyl acrylate to form a triple addition product in good yield, as well as the reaction of diethyl malonate with acrylonitrile to give a double addition product. In this case it was demonstrated that the fullerene probase may be recycled at least two times. The dianion was also used to catalyze the addition of n-octanethiol to styrene oxide. The reactions of still weaker acids could be promoted by the highly basic C{sub 60}{sup 3{minus}}. These included the addition of pyrrole to acrylonitrile and the Wittig-Horner reaction of diethyl benzylphosphonate with benzaldehyde.

  19. Serum high mobility group box 1 protein levels are not associated with either histological severity or treatment response in children and adults with nonalcoholic fatty liver disease

    OpenAIRE

    Yates, Katherine P.; Ross Deppe; Megan Comerford; Howard Masuoka; Cummings, Oscar W.; James Tonascia; Naga Chalasani; Raj Vuppalanchi

    2017-01-01

    Aim Serum high mobility group box 1 protein (HMGB1) is a proinflammatory molecule that could potentially serve as a biomarker for non-alcoholic fatty liver disease (NAFLD) and non-alcoholic steatohepatitis (NASH) due to its correlation with degree of liver fibrosis. The aim of the current study was to examine the cross-sectional and longitudinal relationships between serum HMGB1 levels and liver histology in adults and children with NAFLD participating in two large randomized controlled trial...

  20. Air-stable π-conjugated amorphous copolymer field-effect transistors with high mobility of 0.3 cm2/Vs

    DEFF Research Database (Denmark)

    Georgakopoulos, S.; Gu, Y.; Nielsen, Martin Meedom

    2012-01-01

    We have fabricated organic bottom-contact top-gate field-effect transistors with an indenofluorene-phenanthrene co-polymer semiconductor, exhibiting ON/OFF ratio of 10(7) and uncommonly high mobility for an amorphous conjugated polymer of up to 0.3 cm(2)/Vs. Lack of crystallinity in this material...... transistor mobility is also exceptionally stable in ambient conditions, decreasing only by approximately 15% over two months. (C) 2012 American Institute of Physics...

  1. Scavenging of superoxide anion radical by chaparral.

    Science.gov (United States)

    Zang, L Y; Cosma, G; Gardner, H; Starks, K; Shi, X; Vallyathan, V

    1999-06-01

    Chaparral is considered to act as an antioxidant. However, the inhibitory effects of chaparral on specific radical species are not well understood. Using electron paramagnetic resonance (EPR) spectroscopy in combination with spin trapping techniques, we have found that chaparral scavenges superoxide anion radical (O2*-) in a dose-dependent manner. 5,5-dimethyl-lpyrroline-N-oxide (DMPO) was used as a spin trapping agent and the reaction of xanthine and xanthine oxidase as a source of O2*-. The kinetic parameters, IC50 and Vmax, for chaparral scavenging of O2*- were found to be 0.899 microg/mL and 8.4 ng/mL/sec, respectively. The rate constant for chaparral scavenging O2*- was found to be 1.22 x 10(6) g(-1) s(-1). Our studies suggest that the antioxidant properties of chaparral may involve a direct scavenging effect of the primary oxygen radical, O2*-.

  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. 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.

  4. Thermally dried ink-jet process for 6,13-bis(triisopropylsilylethynyl)-pentacene for high mobility and high uniformity on a large area substrate

    Science.gov (United States)

    Ryu, Gi Seong; Lee, Myung Won; Jeong, Seung Hyeon; Song, Chung Kun

    2012-01-01

    In this study we developed a simple ink-jet process for 6,13-bis(triisopropylsilylethynyl)-pentacene (TIPS-pentacene), which is known as a high-mobility soluble organic semiconductor, to achieve relatively high-mobility and high-uniformity performance for large-area applications. We analyzed the behavior of fluorescent particles in droplets and applied the results to determining a method of controlling the behavior of TIPS-pentacene molecules. The grain morphology of TIPS-pentacene varied depending on the temperature applied to the droplets during drying. We were able to obtain large and uniform grains at 46 degrees C without any "coffee stain". The process was applied to a large-size organic thin-film transistor (OTFT) backplane for an electrophoretic display panel containing 192 x 150 pixels on a 6-in.-sized substrate. The average of mobilities of 36 OTFTs, which were taken from different locations of the backplane, was 0.44 +/- 0.08 cm2.V-1.s-1, with a small deviation of 20%, over a 6-in.-size area comprising 28,800 OTFTs. This process providing high mobility and high uniformity can be achieved by simply maintaining the whole area of the substrate at a specific temperature (46 degrees C in this case) during drying of the droplets.

  5. Thermally Dried Ink-Jet Process for 6,13-Bis(triisopropylsilylethynyl)-Pentacene for High Mobility and High Uniformity on a Large Area Substrate

    Science.gov (United States)

    Ryu, Gi Seong; Lee, Myung Won; Jeong, Seung Hyeon; Song, Chung Kun

    2012-05-01

    In this study we developed a simple ink-jet process for 6,13-bis(triisopropylsilylethynyl)-pentacene (TIPS-pentacene), which is known as a high-mobility soluble organic semiconductor, to achieve relatively high-mobility and high-uniformity performance for large-area applications. We analyzed the behavior of fluorescent particles in droplets and applied the results to determining a method of controlling the behavior of TIPS-pentacene molecules. The grain morphology of TIPS-pentacene varied depending on the temperature applied to the droplets during drying. We were able to obtain large and uniform grains at 46 °C without any “coffee stain”. The process was applied to a large-size organic thin-film transistor (OTFT) backplane for an electrophoretic display panel containing 192×150 pixels on a 6-in.-sized substrate. The average of mobilities of 36 OTFTs, which were taken from different locations of the backplane, was 0.44±0.08 cm2·V-1·s-1, with a small deviation of 20%, over a 6-in.-size area comprising 28,800 OTFTs. This process providing high mobility and high uniformity can be achieved by simply maintaining the whole area of the substrate at a specific temperature (46 °C in this case) during drying of the droplets.

  6. 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...

  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. The a...

  8. 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...

  9. Anion binding by biotin[6]uril in water

    DEFF Research Database (Denmark)

    Lisbjerg, Micke; Nielsen, Bjarne Enrico; Milhøj, Birgitte Olai

    2015-01-01

    In this contribution we show that the newly discovered 6 + 6 biotin-formaldehyde macrocycle Biotin[6]uril binds a variety of anionic guest molecules in water. We discuss how and why the anions are bound based on data obtained using NMR spectroscopy, mass spectrometry, isothermal titration...

  10. 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.

  11. 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.

  12. Enzyme synthesis of kyotorphin precursor in the organic solvent using the surfactant covering enzyme; Kaimen kasseizai hibuku koso wo mochiita yuki yobaichu ni okeru gyotoru fuin zenkutai no koso gosei

    Energy Technology Data Exchange (ETDEWEB)

    Murakami, Yoshihiko; Kawakida, Hidetaka; Hirata, Akira [Waseda University, Tokyo (Japan)

    1999-04-05

    Using surfactant covering enzyme which manifested high activity in the organic solvent, new peptide synthesis technique which separates the product synthesized by enzyme reaction in organic solvent to the water phase in the extraction was proposed. It had anion radical and cationic unit in the molecular structure, and enzyme synthesis reaction of the analgesia peptide kyotorphin (TyrArg) precursor of which the hydrophilicity was a resistant material was taken up, and Z-TyrArgOEt synthesized in the organic solvent phase was selectively separated to the tank in the extraction, and the yield which is higher than the water single phase system a little was achieved. (translated by NEDO)

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

    Energy Technology Data Exchange (ETDEWEB)

    Moyer, Bruce a.; Bostick, Debra A.; Fowler, Christopher J.; Kang, Hyun-Ah; Ruas, Alexandre; Delmau, Laetitia H.; Haverlock, Tamara J.; Llinares, Jose M.; Hossain, Alamgir; Kang, S. O.; Bowman-James, Kristin; Shriver, James A.; Marquez, Manuel; Sessler, Jonathan L.

    2005-09-22

    The major thrust of this project led by the University of Kansas (Prof. Kristin Bowman-Jones) entails the exploration of the principles of recognition and separation of sulfate by the design, synthesis, and testing of novel sulfate extractants. A key science need for the cleanup of tank wastes at Hanford has been identified in developing methods to separate those bulk waste components that have low solubilities in borosilicate glass. Sulfate has been identified as a particularly difficult and expensive problem in that its concentration in the waste is relatively high, its solubility in glass is especially low, and it interferes with the performance of both vitrification equipment and the glass waste form. The new extractants will be synthesized by the University of Kansas and the University of Texas, Austin. Oak Ridge National Laboratory (ORNL) is subjecting the new extractants to experiments that will determine their properties and effectiveness in separating sulfate from the major competing anions in the waste, especially nitrate. Such experiments will entail primarily liquid-liquid extraction. Current efforts focus on exciting new systems in which the anion receptors act as synergists for anion exchange.

  14. AT Base Pair Anions vs. (9-methyl-A)(1-methyl-T) Base Pair Anions

    Energy Technology Data Exchange (ETDEWEB)

    Radisic, Dunja; Bowen, Kit H.; Dabkowska, Iwona; Storoniak, Piotr; Rak, Janusz; Gutowski, Maciej S.

    2005-05-04

    The anionic base pairs of adenine and thymine, (AT)-, and 9-methyladenine and 1-methylthymine, (MAMT)-, have been investigated both theoretically and experimentally in a complementary, synergistic study. Calculations on (AT)- found that it had undergone a barrier-free proton transfer (BFPT) similar to that seen in other dimer anion systems and that its structural configuration that was neither Watson-Crick (WC) nor Hoogsteen (HS). The vertical detachment energy (VDE) of (AT)- was determined by anion photoelectron spectroscopy and found to be in agreement with the VDE value predicted by theory for the BFPT mechanism. An AT pair in DNA is structurally immobilized into the WC configuration, in part, by being bonded to the sugars of the double helix. This circumstance was mimicked by methylating the sites on both A and T where these sugars would have been tied, viz., 9-methyladenine and 1-methylthymine. Calculations found no BFPT in (MAMT)- and a resulting (MAMT)- configuration that wa s either HS or WC, with the configurations differing in stability by ca. 2 kcal/mol. The photoelectron spectrum of (MAMT)- occurred at a completely different electron binding energy than had (AT)-. Moreover, the VDE value of (MAMT)- was in agreement with that predicted by theory. The configuration of (MAMT)- and its lack of electron-induced proton transfer are inter-related. While there may be other pathways for electron-induced damage, BFPT in the WC/HS configurations of (AT)- is not feasible.

  15. Selectivity control in synergistic liquid-liquid anion exchange of univalent anions via structure-specific cooperativity between quaternary ammonium cations and anion receptors.

    Science.gov (United States)

    Borman, Christopher J; Bonnesen, Peter V; Moyer, Bruce A

    2012-10-02

    Two anion receptors enhance liquid-liquid anion exchange when added to quaternary alkylammonium chloride anion exchangers, but with a striking dependence on the structure of the alkylammonium cation that suggests a supramolecular cooperative effect. Two anion receptors were investigated, meso-octamethylcalix[4]pyrrole (C4P) and the bisthiourea tweezer 1,1'-(propane-1,3-diyl)bis(3-(4-sec-butylphenyl)thiourea (BTU). Whereas synergism is comparatively weak when either methyltri(C(8,10))alkylammonium chloride (Aliquat 336) or tetraheptylammonium chloride is used with the BTU receptor, synergism between C4P and Aliquat 336 is so pronounced that anion exchange prefers chloride over more extractable nitrate and trifluoroacetate, effectively overcoming the ubiquitous Hofmeister bias. A thermochemical analysis of synergistic anion exchange has been provided for the first time, resulting in the estimation of binding constants for C4P with the ion pairs of A336(+) with Cl(-), Br(-), OAc(F3)(-), NO(3)(-), and I(-).

  16. Palm oil anionic surfactants based emulsion breaker (Case study of emulsions breaker at Semanggi Field production wells)

    Science.gov (United States)

    Muhpidah; Hambali, E.; Suryani, A.; Kartika, I. A.

    2017-05-01

    The presence of emulsion in oil production process is undesirable. The emulsion will increase the production costs, transportation and costs related to emulsion separation process between water and oil. The development of palm oil-based surfactant as an emulsion breaker needs to be conducted given the availability of abundant raw materials in Indonesia and as an alternative to petroleum-based surfactant. The purpose of this study is to produce palm oil-based emulsion breaker, assessing the effect of additive application to the emulsion breaker and analyze the performance of the emulsion breaker. This research was conducted by formulating palm oil anionic surfactant in water formation with the addition of co-surfactant additive and co-solvent. Palm oil anionic surfactant-based emulsion breaker with 0.5% concentration in water can reduce 50% of emulsions with the interfacial tension (IFT) of 2.33x10-2 dyne/cm. The addition of co-solvent (toluene: xylene) is able to remove the emulsion formed with a lower IFT namely 10-3 dyne / cm. The resulting emulsion breaker is capable to remove the emulsion between water and oil. The performance test of emulsion breaker show that the emulsion is able to maintain its performance at reservoir temperature with no indicate of plugging and the value generated incremental oil recovery values is 13%.

  17. 'Naked-eye' detection of biologically important anions in aqueous media by colorimetric receptor and its real life applications

    Science.gov (United States)

    Singh, Archana; Trivedi, Darshak R.

    2017-05-01

    A colorimetric receptor R 2-[(2-Hydroxy-naphthalen-1-ylmethylene)-hydrazonomethyl]-quinolin-8-ol has been designed and synthesized with good yield and characterized by the standard spectroscopic techniques such as FT-IR, UV-Visible, 1H NMR, 13C NMR and ESI-MS. The receptor R showed naked-eye detection and spectral change in the presence of F-, AcO- and H2PO4- over other anions. Interestingly, receptor R displaying high selective recognition towards F-, AcO- ion with a drastic color change from pale yellow to red in dry DMSO solvent and orange in mixed solvent DMSO/H2O (9:1, v/v). The behavior of receptor R towards F-, AcO- ion was investigated using UV-Vis and 1H NMR experiment. The detailed 1H NMR experiment result revealed that the receptor R is forming the hydrogen bonding between imine nitrogen and phenolic sbnd OH proton towards anions. The receptor R is able to detect sodium salts of flouride (NaF) and acetate (NaAcO) in aqueous medium and it exhibited dramatic color change from pale yellow to red. The receptor R demonstrated itself to be useful for real life application by detecting flouride and acetate ion in sea-water and commercially available product such as toothpaste, mouthwash and vinegar solution.

  18. Cooperativity and complexity in the binding of anions and cations to a tetratopic ion-pair host.

    Science.gov (United States)

    Howe, Ethan N W; Bhadbhade, Mohan; Thordarson, Pall

    2014-05-21

    Cooperative interactions play a very important role in both natural and synthetic supramolecular systems. We report here on the cooperative binding properties of a tetratopic ion-pair host 1. This host combines two isophthalamide anion recognition sites with two unusual "half-crown/two carbonyl" cation recognition sites as revealed by the combination of single-crystal X-ray analysis of the free host and the 1:2 host:calcium cation complex, together with two-dimensional NMR and computational studies. By systematically comparing all of the binding data to several possible binding models and focusing on four different variants of the 1:2 binding model, it was in most cases possible to quantify these complex cooperative interactions. The data showed strong negative cooperativity (α = 0.01-0.05) of 1 toward chloride and acetate anions, while for cations the results were more variable. Interestingly, in the competitive (CDCl3/CD3OD (9:1, v/v)) solvent, the addition of calcium cations to the tetratopic ion-pair host 1 allosterically switched "on" chloride binding that is otherwise not present in this solvent system. The insight into the complexity of cooperative interactions revealed in this study of the tetratopic ion-pair host 1 can be used to design better cooperative supramolecular systems for information transfer and catalysis.

  19. Remediation of Contaminated Soils by Solvent Flushing

    NARCIS (Netherlands)

    Augustijn, Dionysius C.M.; Jessup, Ron E.; Rao, P. Suresh C.; Wood, A. Lynn

    1994-01-01

    Solvent flushing is a potential technique for remediating a waste disposal/spill site contaminated with organic chemicals. This technique involves the injection of a solvent mixture (e.g., water plus alcohols) that enhances contaminant solubility, reduces the retardation factor, and increases the

  20. SOLVENT EFFECTS IN THE HYDROXIDE AND ALKOXIDE ...

    African Journals Online (AJOL)

    in the rationalization or correlation of solvent effects on reaction rates and activation parameters. The objective of the present investigation was to examine the effect of these solvent parameters on the rates of the alkaline decomposition ... metal (,BDH} and methanol, the concentrations were determined by titration.

  1. Molecular Thermodynamic Modeling of Mixed Solvent Solubility

    DEFF Research Database (Denmark)

    Ellegaard, Martin Dela; Abildskov, Jens; O’Connell, John P.

    2010-01-01

    A method based on statistical mechanical fluctuation solution theory for composition derivatives of activity coefficients is employed for estimating dilute solubilities of 11 solid pharmaceutical solutes in nearly 70 mixed aqueous and nonaqueous solvent systems. The solvent mixtures range from ne...

  2. A spreadsheet algorithm for stagewise solvent extraction

    Energy Technology Data Exchange (ETDEWEB)

    Leonard, R.A.; Regalbuto, M.C.

    1993-01-01

    Part of the novelty is the way in which the problem is organized in the spreadsheet. In addition, to facilitate spreadsheet setup, a new calculational procedure has been developed. The resulting Spreadsheet Algorithm for Stagewise Solvent Extraction (SASSE) can be used with either IBM or Macintosh personal computers as a simple yet powerful tool for analyzing solvent extraction flowsheets.

  3. Incorporation of cationic electron donor of Ni-pyridyltetrathiafulvalene with anionic electron acceptor of polyoxometalate.

    Science.gov (United States)

    Tsunashima, Ryo; Matsumoto, Takumi; Hoshino, Norihisa; Niiho, Wataru; Kimura, Mizuki; Kondo, Kei; Suyama, Yoshihiko; Nishioka, Yukihiro; Kawamata, Jun; Noro, Shin-ichiro; Nakamura, Takayoshi; Akutagawa, Tomoyuki; Ishiguro, Katsuya

    2012-09-07

    A new salt-[Ni(II)(DMSO)(5)(TTFPy)](2)[α-SiW(12)O(40)] (1)-based on polyoxometalates was prepared by coordinating a cationic electron donor of pyridyltetrathiafulvalene (TTFPy) with Ni(II). Although the TTFPy molecule did not form a salt with the anionic α-[SiW(VI)(12)O(40)](4-) because of the weak charge-transfer (CT) interaction, the coordination of Ni with the pyridyl moiety permitted salt formation driven by electrostatic interaction, giving a single crystal of 1. Crystallographic analysis, UV-vis and IR spectroscopy and electrochemical characterization revealed that the fully oxidized α-[SiW(VI)(12)O(40)](4-) was crystallized with the neutral TTFPy moiety from the acetonitrile solution because of the low electron-withdrawing ability of α-[SiW(VI)(12)O(40)](4-), forming a brown-orange crystal. The crystal colour quickly turned to black by immersing in methanol, due to CT from TTF moiety to α-[SiW(VI)(12)O(40)](4-), which was caused by the solvent effect. Increase in the solvent acceptor number from 18.9 for acetonitrile to 41.3 for methanol resulted in the enhancement of the electron withdrawing ability of α-[SiW(VI)(12)O(40)](4-) by 0.317 V in methanol.

  4. Iodide and triiodide anion complexes involving anion-π interactions with a tetrazine-based receptor.

    Science.gov (United States)

    Savastano, Matteo; Bazzicalupi, Carla; García, Celeste; Gellini, Cristina; López de la Torre, María Dolores; Mariani, Palma; Pichierri, Fabio; Bianchi, Antonio; Melguizo, Manuel

    2017-04-05

    Protonated forms of the tetrazine ligand L2 (3,6-bis(morpholin-4-ylethyl)-1,2,4,5-tetrazine) interact with iodide in aqueous solution forming relatively stable complexes (ΔG° = -11.6(4) kJ mol(-1) for HL2(+) + I(-) = (HL2)I and ΔG° = -13.4(2) kJ mol(-1) for H2L2(2+) + I(-) = [(H2L2)I](+)). When solutions of [(H2L2)I](+) are left in contact with air, crystals of the oxidation product (H2L2)2(I3)3I·4H2O are formed. Unfortunately, the low solubility of I3(-) complexes prevents the determination of their stability constants. The crystal structures of H2L2I2·H2O (1), H2L2(I3)2·2H2O (2) and (H2L2)2(I3)3I·4H2O (3) were determined by means of X-ray diffraction analyses. In all crystal structures, it was found that the interaction between I(-) and I3(-) with H2L2(2+) is dominated by anion interactions with the π electron density of the receptor. Only in the case of 1, the iodide anions involved in close anion-π interactions with the ligand tetrazine ring form an additional H-bond with the protonated morpholine nitrogen of an adjacent ligand molecule. Conversely, in crystals of 2 and 3 there are alternate segregated planes which contain only protonated ligands hydrogen-bonded to cocrystallized water molecules or I3(-) and I(-) forming infinite two-dimensional networks established through short interhalogen contacts, making these crystalline products good candidates to behave as solid conductors. In the solid complexes, the triiodide anion displays both end-on and side-on interaction modes with the tetrazine ring, in agreement with density functional theory calculations indicating a preference for the alignment of the I3(-) molecular axis with the molecular axis of the ligand. Further information about geometries and structures of triiodide anions in 2 and 3 was acquired by the analysis of their Raman spectra.

  5. Gradient Solvent Vapor Annealing of Thin Films

    Science.gov (United States)

    Albert, Julie; Bogart, Timothy; Lewis, Ronald; Epps, Thomas

    2011-03-01

    The development of block copolymer materials for emerging nanotechnologies requires an understanding of how surface energy/chemistry and annealing conditions affect thin film self-assembly. Specifically, in solvent vapor annealing (SVA), the use of solvent mixtures and the manipulation of solvent vapor concentration are promising approaches for obtaining a desired morphology or nanostructure orientation. We designed and fabricated solvent-resistant devices to produce discrete SVA gradients in composition and/or concentration to efficiently explore SVA parameter space. We annealed copolymer films containing poly(styrene), poly(isoprene), and/or poly(methyl methacrylate) blocks, monitored film thicknesses during annealing, and characterized film morphologies with atomic force microscopy. Morphological changes across the gradients such as the transformation from parallel cylinders to spheres with increasing solvent selectivity provided insight into thin film self-assembly, and the gradient device has enabled us to determine transition compositions and/or concentrations.

  6. Unique effects of the chain lengths and anions of tetra-alkylammonium salts on quenching pyrene excimer.

    Science.gov (United States)

    Jang, Hyun-Sook; Zhao, Jing; Lei, Yu; Nieh, Mu-Ping

    2014-09-10

    Pyrene (Py) excimer, through its unique fluorescence quenching, exhibits high sensitivity and high selectivity in detecting specific electron-deficient molecules, providing a potential platform for sensing technology, optical switch, and probing hydrophobicity of molecular environment. In solution state, its quenching mechanism has been well-studied. However, there remain many unknown properties regarding the quenching mechanism of the solid-state Py excimer. In this paper, the effects of a series of tetra-alkylammonium salts (with a variety of chain lengths and anions) on Py excimer quenching are investigated to identify the controlling parameters of the fluorescence quenching in the binary system. Several experimental approaches including steady-state fluorescence spectroscopy, UV absorption, (13)C-nuclear magnetic resonance (NMR) spectra, X-ray diffraction, scanning electron microscopy, and time-dependent fluorescence decay are employed to seek for the fundamental understanding of the quenching mechanism. The result indicates a unique quenching effect of tetrabutylammonium cation on the pyrene excimer, and which is not observed in the other cations with different chain lengths (the same associated hexafluorophosphate anions). Meanwhile, hexafluorophosphate anion (in the presence of tetrabutylammonium) is able to effectively retain Py excimer fluorescence when the system is prepared by evaporating solvent at high temperature. It is also confirmed that dynamic quenching is involved in the process. Hydrophobic environment around Py molecules shows strong correlation with the formation of Py excimer. The knowledge obtained in this study provides the insights to how the interaction between salt and Py molecule affects the excimer fluorescence.

  7. Preparation a new sorbent based on polymeric ionic liquid for stir cake sorptive extraction of organic compounds and inorganic anions.

    Science.gov (United States)

    Huang, Xiaojia; Wang, Yulei; Hong, Qiuyun; Liu, Yi; Yuan, Dongxing

    2013-11-01

    A new multi-interaction sorbent (MIS) based on polymeric ionic liquid was prepared and used as extractive medium of stir cake sorptive extraction (SCSE). In the presence of dimethyl sulfoxide, an ionic liquid, 1-vinylbenzyl-3-methylimidazolium chloride was used as monomer to copolymerize in situ with divinylbenzene to form the MIS. The influences of the content of monomer and the porogen solvent in the polymerization mixture on the extraction performance were investigated thoroughly. The MIS was characterized by infrared spectroscopy, elemental analysis, scanning electron microscopy and mercury intrusion porosimetry. Parabens and aromatic amines were used to investigate the extraction performance of MIS-SCSE for apolar and strongly polar analytes, respectively. The extraction parameters for parabens and aromatic amines were optimized. At the same time, simple and sensitive analytical methods for parabens and aromatic amines in real samples were developed by the combination of MIS-SCSE and HPLC/DAD. Some inorganic anions, such as F(-), Br(-), NO3(-), PO4(3-) and SO4(2-), were used to test the extraction performance of MIS-SCSE for anions. Results indicated that mechanism involved in the extraction of MIS is the multi-interaction modes including π-π, hydrophobic, hydrogen-bonding, dipole-dipole and anion-exchange interactions. Copyright © 2013 Elsevier B.V. All rights reserved.

  8. THE EFFECT OF SULPHURIC ACID CONCENTRATION ON SOLVENT EXTRACTION OF ReO4 - BY THE LONG-CHAIN ALIPHATIC TERTIARY AMINES AND ALCOHOLS

    Directory of Open Access Journals (Sweden)

    Aleksander G. Kasikov

    2010-06-01

    Full Text Available The effect of sulphuric acid concentration on solvent extraction of ReO4- by the long-chain aliphatic tertiary amines and alcohols in a wide range of H2SO4 concentrations in initial solutions is discussed. It has been established that the influence of the sulphuric acid concentration on rhenium solvent extraction is largely due to the extraction process mechanism. In the case of the anion-exchange mechanism, ReO4- is best extracted from weakly acidic solutions, whereas when the hydrate-solvate mechanism takes place – from solutions containing 4-7 mole/l H2SO4.

  9. The chemistry of nonaqueous solvents v.4 solution phenomena and aprotic solvents

    CERN Document Server

    Lagowski, J J

    1976-01-01

    The Chemistry of Nonaqueous Solvents, Volume IV: Solution Phenomena and Aprotic Solvents focuses on the chemistry of nonaqueous solvents, with emphasis on solution phenomena and aprotic solvents such as tetramethylurea, inorganic acid chlorides, cyclic carbonates, and sulfolane. This book is organized into seven chapters and begins with an overview of the theory of electrical conductivity and elementary experimental considerations, along with some of the interesting research on nonaqueous solvents. It then turns to a discussion on hydrogen bonding phenomena in nonaqueous systems as probed

  10. Predicting the Solubility of Pharmaceutical Cocrystals in Solvent/Anti-Solvent Mixtures

    Directory of Open Access Journals (Sweden)

    Linda Lange

    2016-05-01

    Full Text Available In this work, the solubilities of pharmaceutical cocrystals in solvent/anti-solvent systems were predicted using PC-SAFT in order to increase the efficiency of cocrystal formation processes. Modeling results and experimental data were compared for the cocrystal system nicotinamide/succinic acid (2:1 in the solvent/anti-solvent mixtures ethanol/water, ethanol/acetonitrile and ethanol/ethyl acetate at 298.15 K and in the ethanol/ethyl acetate mixture also at 310.15 K. The solubility of the investigated cocrystal slightly increased when adding small amounts of anti-solvent to the solvent, but drastically decreased for high anti-solvent amounts. Furthermore, the solubilities of nicotinamide, succinic acid and the cocrystal in the considered solvent/anti-solvent mixtures showed strong deviations from ideal-solution behavior. However, by accounting for the thermodynamic non-ideality of the components, PC-SAFT is able to predict the solubilities in all above-mentioned solvent/anti-solvent systems in good agreement with the experimental data.

  11. 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.

  12. ACCELERATED SOLVENT EXTRACTION COMBINED WITH ...

    Science.gov (United States)

    A research project was initiated to address a recurring problem of elevated detection limits above required risk-based concentrations for the determination of semivolatile organic compounds in high moisture content solid samples. This project was initiated, in cooperation with the EPA Region 1 Laboratory, under the Regional Methods Program administered through the ORD Office of Science Policy. The aim of the project was to develop an approach for the rapid removal of water in high moisture content solids (e.g., wetland sediments) in preparation for analysis via Method 8270. Alternative methods for water removal have been investigated to enhance compound solid concentrations and improve extraction efficiency, with the use of pressure filtration providing a high-throughput alternative for removal of the majority of free water in sediments and sludges. In order to eliminate problems with phase separation during extraction of solids using Accelerated Solvent Extraction, a variation of a water-isopropanol extraction method developed at the USGS National Water Quality Laboratory in Denver, CO is being employed. The concentrations of target compounds in water-isopropanol extraction fluids are subsequently analyzed using an automated Solid Phase Extraction (SPE)-GC/MS method developed in our laboratory. The coupled approaches for dewatering, extraction, and target compound identification-quantitation provide a useful alternative to enhance sample throughput for Me

  13. Effect of solvents on the chemical and physical properties of ionic polymer-metal composites

    Science.gov (United States)

    Nemat-Nasser, Sia; Zamani, Shahram; Tor, Yitzhak

    2006-05-01

    Ionic polymer-metal composites (IPMCs) consist of a perfluorinated ionomer membrane (usually Nafion® or Flemion®) plated on both faces with a noble metal such as gold or platinum and neutralized with a certain amount of counterions that balance the electrical charge of anions covalently fixed to the backbone ionomer. IPMCs are electroactive materials with potential applications as actuators and sensors. Their electrical-chemical-mechanical response is dependent on the cations used, the nature and the amount of solvent uptake, the morphology of the electrodes, the composition of the backbone ionomer, the geometry and boundary conditions of the composite element, and the magnitude and spatial and time variation of the applied potential. With water as the solvent, the applied electric potential must be limited to less than 1.3 V at room temperature, to avoid electrolysis. Moreover, water evaporation in open air presents additional problems. These and related factors limit the application of IPMCs with water as the solvent. We present the results of a series of tests on both Nafion- and Flemion-based IPMCs with ethylene glycol, glycerol, and crown ethers as solvents. IPMCs with these solvents have greater solvent uptake and can be subjected to relatively high voltages without electrolysis. They can be actuated in open air for rather long time periods, and at low temperatures. They may be good actuators when high-speed actuation is not necessary. In addition, their slow response in open air allows direct observation of the physical characteristics of the cathode and anode surfaces of a cantilever during actuations. This can provide additional clues for unraveling the underpinning micromechanisms of their actuation. Remarkably, solvents are found to have profound effects on the nature of the IPMCs' actuation. For example, Nafion-based IPMCs in Li+ form show very small back relaxation when hydrated, but extensive back relaxation with all other solvents that we have

  14. Organic Solvent Tolerant Lipases and Applications

    Directory of Open Access Journals (Sweden)

    Shivika Sharma

    2014-01-01

    Full Text Available Lipases are a group of enzymes naturally endowed with the property of performing reactions in aqueous as well as organic solvents. The esterification reactions using lipase(s could be performed in water-restricted organic media as organic solvent(s not only improve(s the solubility of substrate and reactant in reaction mixture but also permit(s the reaction in the reverse direction, and often it is easy to recover the product in organic phase in two-phase equilibrium systems. The use of organic solvent tolerant lipase in organic media has exhibited many advantages: increased activity and stability, regiospecificity and stereoselectivity, higher solubility of substrate, ease of products recovery, and ability to shift the reaction equilibrium toward synthetic direction. Therefore the search for organic solvent tolerant enzymes has been an extensive area of research. A variety of fatty acid esters are now being produced commercially using immobilized lipase in nonaqueous solvents. This review describes the organic tolerance and industrial application of lipases. The main emphasis is to study the nature of organic solvent tolerant lipases. Also, the potential industrial applications that make lipases the biocatalysts of choice for the present and future have been presented.

  15. Environmental Impacts on Nuclear Reprocessing Solvents

    Science.gov (United States)

    Gillens, A. R.; Fessenden, J. E.

    2009-12-01

    Nuclear tests have been employed ever since the first nuclear explosion in Alamogordo, NM during the mid-1940s. Nuclear weapons pose a threat to civil society and result in extensive biological (medical) damages. For this reason, treaties banning nuclear tests and weapons have been employed since the 1960s to cease proliferation of weapons. However, as nuclear tests continue in secrecy and actinides, such as plutonium and uranium, are eligible for theft, nuclear forensics is needed to prevent weapons proliferation. In this study, solvents [tributyl phosphate (TBP), dodecane, decanol] used in reprocessing spent nuclear fuel are analyzed using an isotope ratio mass spectrometer, which provides indisputable evidence in identifying the operation in which solvents were used. Solvent samples are observed under variable conditions in the laboratory for different time periods. It is assumed that their carbon isotope values (δ13C) will become more positive (shift heavy) with time. It is found that the solvents are hygroscopic. TBP leaves the most robust signature compared to the other solvents studied and the isotope values for all solvents under all conditions become more positive with time. This study serves as primary research in understanding how solvents behave under variable conditions in the laboratory and how this could be translated to the environment in fate and transport studies.

  16. Solvent Effect on the Photolysis of Riboflavin.

    Science.gov (United States)

    Ahmad, Iqbal; Anwar, Zubair; Ahmed, Sofia; Sheraz, Muhammad Ali; Bano, Raheela; Hafeez, Ambreen

    2015-10-01

    The kinetics of photolysis of riboflavin (RF) in water (pH 7.0) and in organic solvents (acetonitrile, methanol, ethanol, 1-propanol, 1-butanol, ethyl acetate) has been studied using a multicomponent spectrometric method for the assay of RF and its major photoproducts, formylmethylflavin and lumichrome. The apparent first-order rate constants (k obs) for the reaction range from 3.19 (ethyl acetate) to 4.61 × 10(-3) min(-1) (water). The values of k obs have been found to be a linear function of solvent dielectric constant implying the participation of a dipolar intermediate along the reaction pathway. The degradation of this intermediate is promoted by the polarity of the medium. This indicates a greater stabilization of the excited-triplet states of RF with an increase in solvent polarity to facilitate its reduction. The rate constants for the reaction show a linear relation with the solvent acceptor number indicating the degree of solute-solvent interaction in different solvents. It would depend on the electron-donating capacity of RF molecule in organic solvents. The values of k obs are inversely proportional to the viscosity of the medium as a result of diffusion-controlled processes.

  17. On the effect of ion pairing of Keggin type polyanions with quaternary ammonium cations on redox potentials in organic solvents.

    Science.gov (United States)

    Chen, Bo; Neumann, Ronny

    2016-08-10

    The electrochemical properties of Keggin type polyoxometalates Qn[XW12O40] (X = P, Si, B; Q = n-tetraoctylammonium and n-trioctylmethylammonium) in organic solvents were investigated in order to understand the interrelation between the redox potentials, solvents and ion pairing. A logarithmic correlation between the dielectric constant of the solvent (ε ranged from 4.8 to 46.6) and the reduction potential of the [PW12O4](3-)/[PW12O4](4-) couple was found. This reduction potential increased significantly when the surface charge of the polyoxometalate went from 3- to 5-. The investigation of the ion pairing properties by diffusion NMR revealed the presence of intimate ion pairs in less polar solvents (e.g. dichloromethane) and less compact ion pairs in more polar solvents (e.g. DMSO). Using a V atom within the polyoxometalate an NMR experiment showed that a n-trioctylmethyl ammonium cation bonded to the polyoxometalate anion more intimately than a n-tetraoctyl ammonium cation.

  18. 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)

  19. 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.

  20. Anion, cation, and zwitterion selectivity of phospholemman channel molecules.

    Science.gov (United States)

    Kowdley, G C; Ackerman, S J; Chen, Z; Szabo, G; Jones, L R; Moorman, J R

    1997-01-01

    Phospholemman (PLM), a 72-amino acid membrane protein with a single transmembrane domain, forms taurine-selective ion channels in lipid bilayers. Because taurine forms zwitterions, a taurine-selective channel might have binding sites for both anions and cations. Here we show that PLM channels indeed allow fluxes of both cations and anions, making instantaneous and voltage-dependent transitions among conformations with drastically different ion selectivity characteristics. This surprising and novel ion channel behavior offers a molecular explanation for selective taurine flux across cell membranes and may explain why molecules in the phospholemman family can induce cation- or anion-selective conductances when expressed in Xenopus oocytes. PMID:8994599

  1. Superoxide anion radical scavenging property of catecholamines.

    Science.gov (United States)

    Kładna, Aleksandra; Berczyński, Paweł; Kruk, Irena; Michalska, Teresa; Aboul-Enein, Hassan Y

    2013-01-01

    The direct effect of the four catecholamines (adrenaline, noradrenaline, dopamine and isoproterenol) on superoxide anion radicals (O2•) was investigated. The reaction between 18-crown-6-ether and potassium superoxide in dimethylsulfoxide was used as a source of O2•. The reactivity of catecholamines with O2• was examined using chemiluminescence, reduction of nitroblue tetrazolium and electron paramagnetic resonance spin-trapping techniques. 5,5-Dimethyl-1-pyrroline-N-oxide was included as the spin trap. The results showed that the four catecholamines were effective and efficient in inhibiting chemiluminescence accompanying the potassium superoxide/18-crown-6-ether system in a dose-dependent manner over the range 0.05-2 mM in the following order: adrenaline > noradrenaline > dopamine > isoproterenol, with, IC50 = 0.15 ± 0.02 mM 0.21 ± 0.03 mM, 0.27 ± 0.03 mM and 0.50 ± 0.04 mM, respectively. The catecholamines examined also exhibited a strong scavenging effect towards O2• when evaluated this property by the inhibition of nitroblue tetrazolium reduction (56-73% at 1 M concentration). A very similar capacity of O2• scavenging was monitored in the 5,5-dimethyl-1-pyrroline-N-oxide spin-trapping assay. The results suggest that catecholamines tested may involve a direct effect on scavenging O2- radicals. Copyright © 2013 John Wiley & Sons, Ltd.

  2. Renal transport of organic anions and cations.

    Science.gov (United States)

    Pelis, Ryan M; Wright, Stephen H

    2011-10-01

    Organic anions and cations (OAs and OCs, respectively) comprise an extraordinarily diverse array of compounds of physiological, pharmacological, and toxicological importance. The kidney, primarily the renal proximal tubule, plays a critical role in regulating the plasma concentrations of these organic electrolytes and in clearing the body of potentially toxic xenobiotics agents, a process that involves active, transepithelial secretion. This transepithelial transport involves separate entry and exit steps at the basolateral and luminal aspects of renal tubular cells. Basolateral and luminal OA and OC transport reflects the concerted activity of a suite of separate proteins arranged in parallel in each pole of proximal tubule cells. The cloning of multiple members of several distinct transport families, the subsequent characterization of their activity, and their subcellular localization within distinct regions of the kidney, now allows the development of models describing the molecular basis of the renal secretion of OAs and OCs. New information on naturally occurring genetic variation of many of these processes provides insight into the basis of observed variability of drug efficacy and unwanted drug-drug interactions in human populations. The present review examines recent work on these issues. 2011 American Physiological Society

  3. Series of solvent-induced single-crystal to single-crystal transformations with different sizes of solvent molecules.

    Science.gov (United States)

    He, Yuan-Chun; Yang, Jin; Liu, Ying-Ying; Ma, Jian-Fang

    2014-07-21

    A highly stable soft porous coordination polymer (PCP), namely [Cu3(TP)4(N3)2(DMF)2]·2H2O·2DMF (1), has been synthesized via an in situ synthesis of 4-tetrazole pyridine (TP) under solvothermal conditions (DMF = N,N'-dimethylformamide). Remarkably, the solvent molecules in 1 can be respectively exchanged with cyclohexane (C6H12), cyclopentane (C5H10), decahydronaphthalene (C10H18), 1,4-dioxane (C4H8O2), and tetrahydropyrane (C5H10O) in single-crystal to single-crystal (SCSC) manners to yield [Cu3(TP)4(N3)2(DMF)2]·3C6H12 (1a), [Cu3(TP)4(N3)2(DMF)2]·2C5H10 (1b), [Cu3(TP)4(N3)2(DMF)2]·H2O·C10H18 (1c), [Cu3(TP)4(N3)2(DMF)2]·C4H8O2 (1d), [Cu3(TP)4(N3)2]·3C4H8O2 (1e), and [Cu3(TP)4(N3)2]·2H2O·C5H10O (1f). Further, the occluded cyclohexane molecules in 1a can be removed by heating to give its porous guest-free form [Cu3(TP)4(N3)2(DMF)2] (1g). Particularly, in water, 1 can lose its coordinated N3(-) anions to generate [Cu(TP)2(H2O)4]·4H2O (1h). More interestingly, the soft PCP (1) demonstrates the guest selectivity for the cycloalkane solvents, namely cyclohexane, cyclopentane, and decahydronaphthalene, in SCSC manners for the first time, attributed to the synergy effect between the size and geometry of the solvent and the shape of the framework cavity. Moreover, the desolvated samples of 1e show the highly selective gas adsorption of CO2 over N2, indicating its potential application in the separation of the CO2/N2 mixture.

  4. Physico-chemical properties of Pd nanoparticles produced by Pulsed Laser Ablation in different organic solvents

    Energy Technology Data Exchange (ETDEWEB)

    Cristoforetti, Gabriele, E-mail: gabriele.cristoforetti@cnr.it [National Institute of Optics, Research Area of National Research Council, Via G. Moruzzi 1, 56124 Pisa (Italy); Pitzalis, Emanuela; Spiniello, Roberto [Institute of Chemistry of OrganoMetallic Compounds, Research Area of National Research Council, Via G. Moruzzi 1, 56124 Pisa (Italy); Ishak, Randa [Department of Chem. Eng. And Material Science, University of Pisa, Via Diotisalvi 2, 56126 Pisa (Italy); Giammanco, Francesco [Department of Physics, University of Pisa, Largo B. Pontecorvo 3, 56127 Pisa (Italy); Muniz-Miranda, Maurizio; Caporali, Stefano [Department of Chemistry, University of Florence, Via della Lastruccia 3, 50019 Sesto Fiorentino (Italy)

    2012-01-15

    Palladium nanoparticles are arousing an increasing interest because of their strong activity in heterogeneous catalysis in a wide range of reactions. Driven by the interest of producing Pd nanoparticles to be deposited for catalysis over hydrophobic supports, we investigated their synthesis via Pulsed Laser Ablation in Liquid in several organic solvents, as acetone, ethanol, 2-propanol, toluene, n-hexane. The colloids were produced by using a Nd:YAG ns laser and without the addition of surfactant agents. The morphology, composition, stability and oxidation state of the obtained nanoparticles were investigated by TEM-EDS analysis, UV-vis spectroscopy, X-ray Photoelectron Spectroscopy and micro-Raman spectroscopy. The results evidence that the nature of the solvent influences both the yield and the physico-chemical properties of the produced nanoparticles. While in acetone and alcohols spheroidal, non aggregated and stable particles are obtained, in case of toluene and n-hexane few unstable particles surrounded by a gel-like material are produced. Raman/XPS measurements suggest the presence of amorphous or graphitic carbon onto crystalline Pd nanoparticles, which could have hindered their growth and determined the observed smaller sizes if compared to nanoparticles produced in water. The stability of Pd colloids obtained in acetone and alcohols was attributed to adsorbed anions like enolates or alcoholates; non polar solvents like toluene and n-hexane, unable to give rise to adsorbed anionic species, cannot provide any stabilization to the palladium nanoparticles. XPS analyses also evidenced a partial oxidation of particles surface, with a ratio Pd{sup 2+}:Pd{sup 0} of 1:2.5 and 1:4 in acetone and ethanol, respectively.

  5. Chemical reactions in solvents and melts

    CERN Document Server

    Charlot, G

    1969-01-01

    Chemical Reactions in Solvents and Melts discusses the use of organic and inorganic compounds as well as of melts as solvents. This book examines the applications in organic and inorganic chemistry as well as in electrochemistry. Organized into two parts encompassing 15 chapters, this book begins with an overview of the general properties and the different types of reactions, including acid-base reactions, complex formation reactions, and oxidation-reduction reactions. This text then describes the properties of inert and active solvents. Other chapters consider the proton transfer reactions in

  6. Genomic and Genetic Approaches to Solvent Tolerance

    Energy Technology Data Exchange (ETDEWEB)

    Eleftherios T. Papoutsakis

    2005-06-10

    The proposed research is to understand and exploit the molecular basis that determines tolerance of the industrially important anaerobic clostridia to solvents. Furthermore, we aim to develop general genomic and metabolic engineering strategies for understanding the molecular basis of tolerance to chemicals and for developing tolerant strains. Our hypothesis is that the molecular basis of what makes bacterial cells able to withstand high solvent concentrations can be used to metabolically engineer cells so that they can tolerate higher concentrations of solvents and related chemicals.

  7. A Spreadsheet Algorithm for Stagewise Solvent Extraction

    Energy Technology Data Exchange (ETDEWEB)

    Leonard, R.A.; Regalbuto, M.C.

    1993-08-01

    The material balance and equilibrium equations for solvent extraction processes have been combined with computer spreadsheets in a new way so that models for very complex multicomponent multistage operations can be setup and used easily. A part of the novelty is the way in which the problem is organized in the spreadsheet. In addition, to facilitate spreadsheet setup, a new calculational procedure has been developed. The resulting Spreadsheet Algorithm for Stagewise Solvent Extraction (SASSE) can be used with either IBM or Macintosh personal computers as a simple yet powerful tool for analyzing solvent extraction flowsheets.

  8. Modeling of Salt Solubilities in Mixed Solvents

    DEFF Research Database (Denmark)

    Chiavone-Filho, O.; Rasmussen, Peter

    2000-01-01

    constants and the liquid densities of the solvent media. To normalize the activity coefficients, the symmetric convention is adopted. Thermochemical properties of the salt are used to estimate the solubility product. It is shown that the proposed procedure can describe with good accuracy a series of salt......A method to correlate and predict salt solubilities in mixed solvents using a UNIQUAC+Debye-Huckel model is developed. The UNIQUAC equation is applied in a form with temperature-dependent parameters. The Debye-Huckel model is extended to mixed solvents by properly evaluating the dielectric...

  9. What makes critical-solvent processes work

    Energy Technology Data Exchange (ETDEWEB)

    Brule, M.R.; Corbett, R.W.

    1984-06-01

    Critical-solvent processing (sometimes called supercritical-gas extraction) is an ongoing technology based on phase-equilibrium phenomena in the critical region. Many new practical applications of critical-solvent processing are being conceived and implemented in the food, drug and chemical industries. The advantages afforded by critical-solvent processing in performing difficult separations such as caffeine from coffee, nicotine from tobacco, chemotherapeutic drugs from plants, and chemical feedstocks from petroleum and synfuels residua have been realized just in the last decade or so.

  10. Agglomeration of celecoxib by quasi-emulsion solvent diffusion method without stabilizer: effect of good solvent.

    Science.gov (United States)

    Maghsoodi, Maryam; Nokhodchi, Ali

    2017-01-12

    The aim of the present research is to investigate the feasibility of agglomeration of crystals by the quasi-emulsion solvent diffusion method without using a stabilizer. Two solvent systems comprising a solvent and an antisolvent (water) were used to prepare celecoxib agglomerates. To this end, seven solvents including propanol, methyl acetate, methyl ethyl ketone, butanol, ethyl acetate, isopropyl acetate, and pentanol were examined. The agglomerates were evaluated by micromeritic properties (e.g., size, density, flowability), yield, drug physical state, friability, and dissolution behavior. In the present study the clear trend was observed experimentally in the agglomerate properties as a function of physical properties of the solvent such as miscibility with water. Solvents with high water miscibility (25% v/v) resulted in sticky and hollow particles, while solvents with low water miscibility (3%v/v) led to the formation of agglomerates with low strength. However, the agglomerates made from the solvents with intermediate water miscibility (10% v/v), may reflect a greater integrity of the agglomerates regarding yield and strength. Results of this study offer a useful starting point for a conceptual framework to guide the selection of solvent systems for the quasi-emulsion solvent diffusion method without using a stabilizer.

  11. Immobilization of Anions on Polymer Matrices for Gel Electrolytes with High Conductivity and Stability in Lithium Ion Batteries.

    Science.gov (United States)

    Wang, Shih-Hong; Lin, Yong-Yi; Teng, Chiao-Yi; Chen, Yen-Ming; Kuo, Ping-Lin; Lee, Yuh-Lang; Hsieh, Chien-Te; Teng, Hsisheng

    2016-06-15

    This study reports on a high ionic-conductivity gel polymer electrolyte (GPE), which is supported by a TiO2 nanoparticle-decorated polymer framework comprising poly(acrylonitrile-co-vinyl acetate) blended with poly(methyl methacrylate), i.e. , PAVM: TiO2. High conductivity TiO2 is achieved by causing the PAVM:TiO2 polymer framework to swell in 1 M LiPF6 in carbonate solvent. Raman analysis results demonstrate that the poly(acrylonitrile) (PAN) segments and TiO2 nanoparticles strongly adsorb PF6(-) anions, thereby generating 3D percolative space-charge pathways surrounding the polymer framework for Li(+)-ion transport. The ionic conductivity of TiO2 is nearly 1 order of magnitude higher than that of commercial separator-supported liquid electrolyte (SLE). TiO2 has a high Li(+) transference number (0.7), indicating that most of the PF6(-) anions are stationary, which suppresses PF6(-) decomposition and substantially enlarges the voltage that can be applied to TiO2 (to 6.5 V vs Li/Li(+)). Immobilization of PF6(-) anions also leads to the formation of stable solid-electrolyte interface (SEI) layers in a full-cell graphite|electrolyte|LiFePO4 battery, which exhibits low SEI and overall resistances. The graphite|electrolyte|LiFePO4 battery delivers high capacity of 84 mAh g(-1) even at 20 C and presents 90% and 71% capacity retention after 100 and 1000 charge-discharge cycles, respectively. This study demonstrates a GPE architecture comprising 3D space charge pathways for Li(+) ions and suppresses anion decomposition to improve the stability and lifespan of the resulting LIBs.

  12. One-step selective electrokinetic removal of inorganic anions from small volumes and its application as sample clean-up for mass spectrometric techniques.

    Science.gov (United States)

    Tubaon, Ria Marni; Haddad, Paul R; Quirino, Joselito P

    2017-03-10

    The presence of inorganic anions in a sample interferes with mass spectrometric (MS) analysis. Here, a simple method to remove these ions from a liquid sample in one-step is described. The inorganic anions present in a 50μL sample were extracted into a low pH solution inside a 200μm i.d.×33cm long capillary by the use of an electric field. The selective removal of unwanted anions and retention of target analytes was accomplished by control of the apparent electrophoretic velocities of anions and analytes at a boundary that separated the sample and extraction solution. No physical barrier (e.g., membrane) was required and with the boundary situated at the tip of the capillary, efficient removal of inorganic anions (e.g., >80% removal) and good recovery of target analytes (e.g., >80% recovery) were achieved. The time required for removal of the inorganic anions was found to depend on their initial concentrations. The removal process was investigated using different concentrations of bromide and nitrate (as potassium salts) and negatively chargeable drugs as target analytes. This micro-sample clean-up technique used no organic solvents and little consumables and was studied to the determination of 0.6μg/L arsenic and 8.3μg/L vanadium in 500mg/L sodium chloride using inductively coupled plasma MS and 50μM angiotensin I in 1000mg/L sodium chloride using electrospray ionisation MS. Micro-sample clean-up was performed for 45min at 3kV in both demonstrations. The calculated recoveries for the metals at trace levels were 110-130%, and for the peptide was 103.8%. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Mutagenesis of the HMGB (high-mobility group B) protein Cmb1 (cytosine-mismatch binding 1) of Schizosaccharomyces pombe: effects on recognition of DNA mismatches and damage.

    OpenAIRE

    Kunz, Christophe; Zurbriggen, Karin; Fleck, Oliver

    2003-01-01

    Cmb1 (cytosine-mismatch binding 1) is a high-mobility group (HMG) protein of Schizosaccharomyces pombe, which consists of 223 amino acids and has a single HMG domain at the C-terminal end. We have created several mutant and deletion forms of the Cmb1 protein and studied the effects on general DNA binding and specific binding to DNA mismatches and damaged DNA. Cmb1Delta41 (i.e. Cmb1 from which the 41 N-terminal amino acids have been deleted) bound specifically to cytosine-containing mismatches...

  14. A comparison of high-mobility group-box 1 protein, lipopolysaccharide-binding protein and procalcitonin in severe community-acquired infections and bacteraemia: a prospective study

    DEFF Research Database (Denmark)

    Gaïni, Shahin; Koldkjaer, Ole G; Møller, Holger J

    2008-01-01

    INTRODUCTION: High-mobility group box-1 protein (HMGB1) has been known as a chromosomal protein for many years. HMGB1 has recently been shown to be a proinflammatory cytokine with a role in the immunopathogenesis of sepsis. Lipopolysaccharide-binding protein (LBP) has a central role in the innate...... cell count and neutrophils) were measured with commercially available laboratory techniques. RESULTS: A total of 185 adult patients were included in the study; 154 patients fulfilled our definition of infection. Levels of HMGB1, LBP and PCT were higher in infected patients compared with a healthy...

  15. Synthesis and redox properties of triarylmethane dye cation salts of anions [M6O19]2- (M = Mo, W).

    Science.gov (United States)

    Guo, Si-Xuan; Xie, Jingli; Gilbert-Wilson, Ryan; Birkett, Stephen L; Bond, Alan M; Wedd, Anthony G

    2011-01-14

    Four salts have been isolated combining the triarylmethane dye cations pararosaniline (PR(+)) and crystal violet (CV(+)) with the hexametalates [M(6)O(19)](2-) (M = Mo, W). A new hexatungstic acid H(2)[W(6)O(19)]·4dma (dma = dimethylacetamide) was isolated and is a useful synthon for hexatungstate salts. Single-crystal X-ray diffraction confirmed the presence of PR(+) and [Mo(6)O(19)](2-) ions in [PR](2)[Mo(6)O(19)]·6dmf (dmf = dimethylformamide). A number of charge-assisted hydrogen bonds N-H···O exist between the cation -NH(2) functions and the anion oxygen atoms. Comparative cyclic voltammetry of salts [A]Cl (A = PR, CV), [Bu(4)N](2)[M(6)O(19)](2-) and A(2)[M(6)O(19)] was established in MeCN and Me(2)SO solutions and of solids in contact with the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide [emim][tfsa]. In the molecular solvents, the reversible potential for the process [Mo(6)O(19)](2-/3-) is less negative than the first reduction processes of the dye cations. In contrast, that for [W(6)O(19)](2-/3-) is more negative. Spectro-electrochemistry and bulk electrolysis experiments reveal significantly different pathways in the two cases. In contrast, in the [emim][tfsa] medium, a positive shift in reduction potential of at least 400 mV is seen for the anion processes but relatively little change for the dye cation processes. This means that initial reduction of the anions always precedes that of the dyes, providing significant simplification of the complex voltammetric data. Chemically modified electrodes can be used in the ionic liquid because of slow dissolution kinetics. However, reduced anion salts dissolve rapidly, allowing dissolved phase electrochemistry to be examined. The electrochemistries of the oxidized salts A(2)[M(6)O(19)] are essentially those of the individual ions, although low level interaction of A(+) with reduced anions [M(6)O(19)](3-,4-) is evident. The work establishes protocols for synthesis and handling of

  16. Fast determination of anions on a short coated column.

    Science.gov (United States)

    Li, Jing; Zhu, Yan; Guo, Yingying

    2006-06-16

    In this paper, a simple method for the separation and determination of common inorganic anions by fast ion-exchange chromatography, using a modified short (25 mm x 4.6 mm) monolithic column, is reported. Coating the column with a cationic surfactant, cetylpyridinium chloride (CPC), the isocratic separation of some inorganic anions in minutes was possible, by direct or indirect UV detection. The coated column demonstrated excellent stability over time, even at a high flow-rate, giving retention times with an average relative standard deviation of 1.3% for over 10 consecutive runs. The developed column exhibited unusual selectivity for common anions, was successfully applied to the rapid analysis of inorganic anions of food samples, river water and factory waste water samples.

  17. 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.

  18. 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.

  19. New anion-exchange polymers for improved separations

    Energy Technology Data Exchange (ETDEWEB)

    Jarvinen, G.D.; Barr, M.E.; Marsh, S.F.

    1997-08-01

    Objective is to improve the understanding of how the structure of a new class of anion-exchange polymers controls the binding of anionic actinide complexes from solution. This is needed to develop practical separation systems that will reduce the cost of actinide processing operations within the DOE complex. In addition anion exchange is widely used in industry. Several new series of bifunctional anion- exchange polymers have been designed, synthesized, and tested for removing Pu(IV), Am(III), and U(VI) from nitric acid. The polymers contain a pyridinium site derived from the host poly(4-vinylpyridine) and a second cationic site attached through a chain of 2 to 6 methylene groups. The new polymers removed Pu four to ten times more efficiently than the best commercial materials.

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

    DEFF Research Database (Denmark)

    Stephansen, Anne Boutrup

    -puckering of the nucleobases. In certain cases specific ring-puckering can stabilize the valence-anions to prolong their lifetimes significantly, even when formed in the scattering continuum. The study of cation dynamics aims at understanding peculiar isotope effects in the decomposition of ionized dihaloalkanes. Br...... electrons and subsequently transition from dipole to valence-bound anions in different energy regimes. The investigations indicate that dipole-bound anion formation depends strongly on the magnitude of the molecular dipole moment, while the formation and stability of valence-bound anions depends on ring......-C-Br bending is activated by pump-induced ionization, which shows up as oscillating ion transitions arising from probe-induced fragmentation. The source of the isotopic preference is analyzed by tracking temporal changes in the contribution from each isotopomer to the total fragment-ion signal. Preliminary...

  1. 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.

  2. 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...

  3. Anionic solid lipid nanoparticles supported on protamine/DNA complexes

    Science.gov (United States)

    Ye, Jiesheng; Wang, Aihua; Liu, Chunxi; Chen, Zhijin; Zhang, Na

    2008-07-01

    The objective of this study was to design novel anionic ternary nanoparticles for gene delivery. These ternary nanoparticles were equipped with protamine/DNA binary complexes (150-200 nm) as the support, and the anionic formation was achieved by absorption of anionic solid lipid nanoparticles (lipofectamine. The transfection efficiency of the ternary nanoparticles was better than that of naked DNA and the binary complexes, and almost equal to that of lipofectamine/DNA complexes, as revealed by inversion fluorescence microscope observation. These results indicated that the anionic ternary nanoparticles could facilitate gene transfer in cultured cells, and might alleviate the drawbacks of the conventional cationic vector/DNA complexes for gene delivery in vivo.

  4. Ion-exchange concentration of inorganic anions from aqueous solution

    Directory of Open Access Journals (Sweden)

    L. P. Bondareva

    2016-01-01

    Full Text Available Monitoring of natural waters in the present time - consuming process, the accuracy of which is influenced by many factors: the composition of water, the presence of impurities and "interfering" components. The water sample preparation process includes the step of concentration and separation of ions determined. The most versatile, efficient, and frequently used method is the concentration of inorganic anions from aqueous solutions by ion exchanger, which can optimize the composition of water to the optimal for identification and quantitative determination of anions. The characteristics of sorption chloride, nitrate and sulfate ions of basic anion exchange resin AВ-17 and Purolite A430 were compared in the article. The constants of protolysis of ion exchangers both AB 17 and Purolite A430 are the same and equal 0.037 ± 0,002. The value of total capacity (POE Purolite A430 was 4.3 mmol/g, AB 17 – 3.4 mmol/g. The studied ion exchangers have the same type of ionic groups – quaternary ammonium, but their number and denotes differ. The number of quaternary ammonium groups is higher in Purolite A430, respectively the number of absorbed anions of these ion exchanger is higher. The values of dynamic exchange capacity (DOE of ion exchanger Purolite A430 is higher than these values of AB-17 and equal to 1.48 ± 0.03 mmol / dm3 for chloride ion, 1.50 ± 0.03 mmol / dm3 for nitrate ion, 1.62 ± 0.03 mmol / dm3 for sulfate ion. The values of the POE and DOE of anion-exchange resins Purolite A430 and AV-17 and the characteristics of the individual sorption of chloride, nitrate, sulfate ions showed an advantage of the Purolite for the concentrationing of anions. It is found that times of anions sorption from triple-anion solutions by Purolite A430 are significantly different for different anions, and these times are close for anion-exchanger AV-17. It proves the possibility of quantitative separation and concentration by anion-exchanger Purolite A430.

  5. Anion exchange membranes composed of a poly(2,6-dimethyl-1,4-phenylene oxide) random copolymer functionalized with a bulky phosphonium cation

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Ye; Zhang, Bingzi; Kinsinger, Corey L.; Yang, Yuan; Seifert, Soenke; Yan, Yushan; Mark Maupin, C.; Liberatore, Matthew W.; Herring, Andrew M.

    2016-05-01

    A random copolymer, tris(2,4,6-trimethoxyphenyl) phosphonium functionalized poly(2,6-dimethyl-1,4-phenylene oxide) (PPO-TPQP) was cast from three different solvents: dimethyl sulfoxide (DMSO), ethyl lactate, or a 41:59 vol% mixture of DMSO and ethyl lactate. Solvents were selected via analysis of the Hansen solubility parameters to vary the phase separation of the polymer in the films. An optimized mixture of DMSO and ethyl lactate chosen for film fabrication and this film was contrasted with films cast from the neat constituent solvents. Atomic force microscopy identified domains from nanometer to tens of nanometer sizes, while the light microscopy showed features on the order of micron. SAXS revealed a cation scattering peak with a d-spacing from 7 to 15 A. Trends in conductivity and water diffusion for the membranes vary depending on the solvent from which they are cast. The mixed solvent cast membrane shows a linear Arrhenius behavior indicating fully dissociated cationic/anionic groups, and has the highest bromide conductivity of 3 mS/cm at 95% RH, 90 degrees C. The ethyl lactate cast membrane shows a linear Arrhenius relation in conductivity, but a Vogel-Tamman-Fulcher behavior in its water self-diffusion. While water increases bromide dissociation, water and bromide transport in these films seems to be decoupled. This is particularly true for the film cast from ethyl lactate.

  6. Solvent induced supramolecular anisotropy in molecular gels

    Energy Technology Data Exchange (ETDEWEB)

    Rogers, Michael A., E-mail: mroger09@uoguelph.ca [Department of Food Science, University of Guelph, Guelph, Ontario, N3C3X9 (Canada); Corradini, Maria G. [Department of Food Science, University of Massachusetts Amherst, Amherst, MA, 01003 (United States); Emge, Thomas [Department of Chemistry and Biochemistry, Rutgers University, New Brunswick, NJ, 08901 (United States)

    2017-06-15

    Herein is the first report of solvent induced anisotropy in 12-hydroxystearic acid self-assembled fibrillar networks. Increasing the chain length of polar solvent, such as nitriles and ketones, tailored the anisotropy of the fibrillar aggregates. 12HSA molecular gels, comprised of alkanes, exhibited an isotropic fibrillar network irrespective of the alkane chain length. In polar solvents, anisotropy, observed using 2D powder x-ray diffraction profiles, is correlated to a fibrillar supramolecular morphologies in long chain nitriles and ketones while sphereulitic crystals are correlated to x-ray diffraction patterns with an isotropic scatter intensity in short chain ketones and nitriles. These changes directly modify the final physical properties of the gels. - Highlights: • 12-HSA self-assembles into crystalline supramolecular morphologies depending on the solvent. • Alkanes, short chain nitriles and ketones led to 12-HSA displaying supramolecular isotropy. • In long chain nitriles and ketones, 12-HSA displays supramolecular anisotropy.

  7. Computer-aided solvent screening for biocatalysis

    NARCIS (Netherlands)

    Abildskov, J.; Leeuwen, van M.B.; Boeriu, C.G.; Broek, van den L.A.M.

    2013-01-01

    A computer-aidedsolventscreening methodology is described and tested for biocatalytic systems composed of enzyme, essential water and substrates/products dissolved in a solvent medium, without cells. The methodology is computationally simple, using group contribution methods for calculating

  8. Computer-Aided Solvent Screening for Biocatalysis

    DEFF Research Database (Denmark)

    Abildskov, Jens; Leeuwen, M.B. van; Boeriu, C.G.

    2013-01-01

    constrained properties related to chemical reaction equilibrium, substrate and product solubility, water solubility, boiling points, toxicity and others. Two examples are provided, covering the screening of solvents for lipase-catalyzed transesterification of octanol and inulin with vinyl laurate...

  9. SHORT COMMUNICATION SOLVENT FREE PREPARATION OF N ...

    African Journals Online (AJOL)

    Preferred Customer

    carboxy, 4-bromo, 4- hydroxy, 3-hydroxy, 4-chloro and ... KEYWORDS: Solvent free, Maleanilic acids, Maleic anhydride, Aniline derivatives ... vibration, also referred to as the amide II bands and are characterized to primary and secondary amide [16].

  10. Solvent selectivity studies using isomers of polystyrene

    Energy Technology Data Exchange (ETDEWEB)

    Men, L.C.; Na, H.; Rogers, L.B.

    1984-01-01

    The order of elution of isomeric trimers of polystyrene has been found to be independent of the dominant solvent-solute interaction as indicated by the location of the solvent in a Snyder triangle. The pure solvents were nitromethane, propylene carbonate, N-methylformamide, acetonitrile, the mixtures were trifluoroethanol with chloroform, methylene chloride and trichlorotrifluoroethane and also one of 2-methoxyethanol with water. Likewise, mixtures of acetonitrile with solvents near each of the corners of that triangle (chloroform, methylene chloride, and trifluoroethanol did not change the order of isomer elution). Substitution of trifluoroethanol for ethanol in mixtures with chloroform, methylene chloride, or trichlorotrifluoroethane led to improved isomer fractionations. 3 references, 5 figures, 2 tables.

  11. 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....

  12. 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

  13. 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...complexity and carbonate formation. Anion exchange membrane (AEMs) fuel cells have a number of advantages over both PEM fuel cells and traditional AFCs...release; distribution is unlimited. (Invited) Thin Robust Anion Exchange Membranes for Fuel Cell Applications The views, opinions and/or findings

  14. Identification of protein–protein interfaces by decreased amide proton solvent accessibility

    Science.gov (United States)

    Mandell, Jeffrey G.; Falick, Arnold M.; Komives, Elizabeth A.

    1998-01-01

    Matrix-assisted laser desorption ionization–time-of-flight mass spectrometry was used to identify peptic fragments from protein complexes that retained deuterium under hydrogen exchange conditions due to decreased solvent accessibility at the interface of the complex. Short deuteration times allowed preferential labeling of rapidly exchanging surface amides so that primarily solvent accessibility changes and not conformational changes were detected. A single mass spectrum of the peptic digest mixture was analyzed to determine the deuterium content of all proteolytic fragments of the protein. The protein–protein interface was reliably indicated by those peptides that retained more deuterons in the complex compared with control experiments in which only one protein was present. The method was used to identify the kinase inhibitor [PKI(5–24)] and ATP-binding sites in the cyclic-AMP-dependent protein kinase. Three overlapping peptides identified the ATP-binding site, three overlapping peptides identified the glycine-rich loop, and two peptides identified the PKI(5–24)-binding site. A complex of unknown structure also was analyzed, human α-thrombin bound to an 83-aa fragment of human thrombomodulin [TMEGF(4–5)]. Five peptides from thrombin showed significantly decreased solvent accessibility in the complex. Three peptides identified the anion-binding exosite I, confirming ligand competition experiments. Two peptides identified a new region of thrombin near the active site providing a potential mechanism of how thrombomodulin alters thrombin substrate specificity. PMID:9843953

  15. Computer-Aided Solvent Screening for Biocatalysis

    OpenAIRE

    Abildskov, Jens; Leeuwen, M.B. van; Boeriu, C.G.; Broek, L.A.M. van den

    2013-01-01

    A computer-aided solvent screening methodology is described and tested for biocatalytic systems composed of enzyme, essential water and substrates/products dissolved in a solvent medium, without cells. The methodology is computationally simple, using group contribution methods for calculating constrained properties related to chemical reaction equilibrium, substrate and product solubility, water solubility, boiling points, toxicity and others. Two examples are provided, covering the screening...

  16. Hydrogen recovery by novel solvent systems

    Energy Technology Data Exchange (ETDEWEB)

    Shinnar, R.; Ludmer, Z.; Ullmann, A.

    1991-08-01

    The objective of this work is to develop a novel method for purification of hydrogen from coal-derived synthesis gas. The study involved a search for suitable mixtures of solvents for their ability to separate hydrogen from the coal derived gas stream in significant concentration near their critical point of miscibility. The properties of solvent pairs identified were investigated in more detail to provide data necessary for economic evaluation and process development.

  17. Comparison of reversed-phase/cation-exchange/anion-exchange trimodal stationary phases and their use in active pharmaceutical ingredient and counterion determinations.

    Science.gov (United States)

    Liu, Xiaodong; Pohl, Christopher A

    2012-04-06

    This study involved three commercial reversed-phase (RP)/anion-exchange (AEX)/cation-exchange (CEX) trimodal columns, namely Acclaim Trinity P1 (Thermo Fisher Scientific), Obelisc R (SIELC Technologies) and Scherzo SM-C18 (Imtakt). Their chromatographic properties were compared in details with respect to hydrophobicity, anion-exchange capacity, cation-exchange capacity, and selectivity, by studying retention behavior dependency on organic solvent, buffer concentration and pH. It was found that their remarkably different column chemistries resulted in distinctive chromatography properties. Trinity P1 exhibited strong anion-exchange and cation-exchange interactions but low RP retention while Scherzo SM-C18 showed strong reversed-phase retention with little cation-exchange and anion-exchange capacities. For Obelisc R, its reversed-phase capacity was weaker than Scherzo SM-C18 but slightly higher than Trinity P1, and its ion-exchange retentions were between Trinity P1 and Scherzo SM-C18. In addition, their difference in selectivity was demonstrated by examples of determining the active pharmaceutical ingredient (API) and counterion of drug products. Copyright © 2011 Elsevier B.V. All rights reserved.

  18. 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.

  19. Solvent Extraction and Ion Exchange in Radiochemistry

    Science.gov (United States)

    Skarnemark, G.

    In 1805, Bucholz extracted uranium from a nitric acid solution into ether and back-extracted it into pure water. This is probably the first reported solvent-extraction investigation. During the following decades, the distribution of neutral compounds between aqueous phases and pure solvents was studied, e.g., by Peligot, Berthelot and Jungfleisch, and Nernst. Selective extractants for analytical purposes became available during the first decades of the twentieth century. From about 1940, extractants such as organophosphorous esters and amines were developed for use in the nuclear fuel cycle. This connection between radiochemistry and solvent-extraction chemistry made radiochemists heavily involved in the development of new solvent extraction processes, and eventually solvent extraction became a major separation technique in radiochemistry. About 160 years ago, Thompson and Way observed that soil can remove potassium and ammonium ions from an aqueous solution and release calcium ions. This is probably the first scientific report on an ion-exchange separation. The first synthesis of the type of organic ion exchangers that are used today was performed by Adams and Holmes in 1935. Since then, ion-exchange techniques have been used extensively for separations of various radionuclides in trace as well as macro amounts. During the last 4 decades, inorganic ion exchangers have also found a variety of applications. Today, solvent extraction as well as ion exchange are used extensively in the nuclear industry and for nuclear, chemical, and medical research. Some of these applications are discussed in the chapter.

  20. CHEMICAL STABILITY OF POLYPHENYLENE SULFIDE IN THE NEXT GENERATION SOLVENT FOR CAUSTIC-SIDE SOLVENT EXTRACTION

    Energy Technology Data Exchange (ETDEWEB)

    Fondeur, F.; Fink, S.

    2011-12-08

    The Office of Waste Processing, within the Office of Technology Innovation and Development, is funding the development of an enhanced solvent for deployment at the Savannah River Site for removal of cesium from High Level Waste. For simplicity, this solvent is referred to as the Next Generation Solvent (NGS). The technical effort is collaboration between Oak Ridge National Laboratory (ORNL), Savannah River National Laboratory (SRNL), and Argonne National Laboratory. The initial deployment target envisioned for the technology was within the Modular Caustic-Side Solvent Extraction Unit (MCU). Deployment of a new chemical within an existing facility requires verification that the chemical components are compatible with the installed equipment. In the instance of a new organic solvent, the primary focus is on compatibility of the solvent with polyphenylene sulfide (PPS), the polymer used in the coalescers within MCU. This report provides the data from exposing PPS polymer to NGS. The test was conducted over a three month period. PPS is remarkably stable in the presence of the next generation solvent. Testing showed no indication of swelling or significant leaching. Preferential sorption of the Modifier on PPS was observed but the same behavior occurs with the baseline solvent. Therefore, PPS coalescers exposed to the NGS are expected to perform comparably to those in contact with the baseline solvent.

  1. PSE For Solvent Applications: A Generic Computer-aided Solvent Selection and Design Framework

    DEFF Research Database (Denmark)

    Mitrofanov, Igor; Sin, Gürkan; Gani, Rafiqul

    system engineering view that emphasizes a systematic and generic solution framework to solvent selection problems is presented. The framework integrates different methods and tools to manage the complexity and solve a wide range of problems in efficient and flexible manner. Its software implementation...... industry (API solubility), solvents i! ! n formulations and as cleaning agents. The template is expected to guide the average user through the essential and desirable steps in solvent selection and design. The expert may also use the general interface and create their own template for the types of solvent...

  2. H and Au diffusion in high mobility a-InGaZnO thin-film transistors via low temperature KrF excimer laser annealing

    Science.gov (United States)

    Bermundo, Juan Paolo S.; Ishikawa, Yasuaki; Fujii, Mami N.; Ikenoue, Hiroshi; Uraoka, Yukiharu

    2017-03-01

    We report the fabrication of high mobility amorphous InGaZnO (a-IGZO) thin-film transistors (TFTs) irradiated by a single shot of a 248 nm KrF excimer laser. Very high mobilities (μ) of up to 43.5 cm2/V s were obtained after the low temperature excimer laser annealing (ELA) process. ELA induces high temperatures primarily in the upper layers and maintains very low temperatures of less than 50 °C in the substrate region. Scanning Transmission Electron micrographs show no laser induced damage and clear interfaces after the laser irradiation. In addition, several characterization studies were performed to determine the μ improvement mechanism. The analysis of Secondary Ion Mass Spectrometry and X-ray Photoelectron Spectroscopy suggests incorporation of H mainly from the hybrid passivation layer into the channel. Moreover, Energy-dispersive X-ray Spectroscopy results show that Au diffused into the channel after ELA. Both KrF ELA-induced H and Au diffusion contributed to the higher μ. These results demonstrate that ELA can greatly enhance the electrical properties of a-IGZO TFTs for promising applications in large area, transparent, and flexible electronics.

  3. A novel missense mutation in the high mobility group domain of SRY drastically reduces its DNA-binding capacity and causes paternally transmitted 46,XY complete gonadal dysgenesis.

    Science.gov (United States)

    Filges, Isabel; Kunz, Christophe; Miny, Peter; Boesch, Nemya; Szinnai, Gabor; Wenzel, Friedel; Tschudin, Sibil; Zumsteg, Urs; Heinimann, Karl

    2011-10-01

    To investigate the familial segregation, role, and function of a novel SRY missense mutation c.347T>C in two half-sisters affected by 46,XY complete gonadal dysgenesis (CDG) compatible with a successful pregnancy outcome. Phenotypic, mutational, and functional study. Academic research unit. Two half-sisters, their common father, and 100 healthy control individuals. Chromosome, molecular cytogenetic analysis, and Sanger sequencing of the SRY gene in blood lymphocytes of the proband, her affected half-sister, and in inflammatory tissue of the father postmortem. Cloning and expression of high mobility group box carboxy-terminal domains of Sry and electrophoretic mobility shift assay were performed. Not applicable. A novel SRY missense mutation c.347T>C (p.Leu116Ser) was identified in two half-sisters and segregates with the CGD phenotype. It is present in the common healthy father in a mosaic state. Functional analyses demonstrate the pathogenic effect of the mutation by a strong reduction of DNA affinity for the mutant p.Leu116Ser SRY protein. The missense mutation c.347T>C in the high mobility group domain of SRY causes 46,XY CGD. Paternal gonadal mosaicism is likely to explain the familial occurrence of 46,XY CGD suggesting a de novo mutational event during the early stages of embryonic development. This novel mutation is compatible with a successful pregnancy outcome. Copyright © 2011 American Society for Reproductive Medicine. Published by Elsevier Inc. All rights reserved.

  4. Overexpression of the truncated form of High Mobility Group A proteins (HMGA2) in human myometrial cells induces leiomyoma-like tissue formation.

    Science.gov (United States)

    Mas, Aymara; Cervelló, Irene; Fernández-Álvarez, Ana; Faus, Amparo; Díaz, Ana; Burgués, Octavio; Casado, Marta; Simón, Carlos

    2015-04-01

    The pathogenesis of uterine leiomyomas, the most common benign tumor in women, is still unknown. This lack of basic knowledge limits the development of novel non-invasive therapies. Our group has previously demonstrated that leiomyoma side population (SP) cells are present in tumor lesions and act like putative tumor-initiating stem cells in human leiomyoma. Moreover, accumulated evidence demonstrates that these benign tumors of mesenchymal origin are characterized by rearrangements of the High Mobility Group A proteins (HMGA). In this work, we tested the hypothesis that leiomyoma development may be due to overexpression of HMGA2 (encoding high mobility group AT-hook2) in myometrial stem cells using in vitro and in vivo approaches. Our work demonstrates that the truncated/short form of HMGA2 induces myometrial cell transformation toward putative tumor-initiating leiomyoma cells and opens up new possibilities to understand the origin of leiomyomas and the development of new therapeutic approaches. © The Author 2014. Published by Oxford University Press on behalf of the European Society of Human Reproduction and Embryology. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  5. Cleanup and analysis of sugar phosphates in biological extracts by using solid phase extraction and anion-exchange chromatography with pulsed amperometric detection

    DEFF Research Database (Denmark)

    Smith, Hans Peter; Cohen, A.; Buttler, T.

    1998-01-01

    of Saccharomyces cerevisiae obtained by using cold methanol as quenching agent and chloroform as extraction solvent. It was shown that pretreatment of the cell extract with SPE markedly improved the quality of the liquid chromatography analysis with recoveries of the sugar phosphates close to 100%. Furthermore......A cleanup method based on anion-exchange solid-phase extraction (SPE) was developed to render biological extracts suitable for the analysis of hexose phosphates with a modified anion-exchange chromatography method and pulsed amperometric detection. The method was applied to cell extracts......, the method allowed for sample enrichment and the original extraction procedure could be simplified by implementing SPE early in the extraction protocol. (C) 1998 Academic Press....

  6. Anion-macrodipole interactions: self-assembling oligourea/amide macrocycles as anion transporters that respond to membrane polarization.

    OpenAIRE

    Hennig Andreas; Fischer Lucile; Guichard Gilles; Matile Stefan

    2009-01-01

    Macrocyclic urea/amide hybrids are introduced as functional anion selective membrane transporters in lipid bilayer membranes. Six derivatives with varying side chains (aliphatic and aromatic) and conformations (parallel and antiparallel carbonyl dipoles) are investigated by fluorescence methods among which the more active aromatic derivatives were selected for an in depth study. Strong response of transport activity toward anion exchange and weak response toward cation exchange establish anio...

  7. Transient Raman spectra, structure, and thermochemistry of the thiocyanate dimer radical anion in water.

    Science.gov (United States)

    Janik, Ireneusz; Carmichael, Ian; Tripathi, G N R

    2017-06-07

    Time-resolved resonance-enhanced Stokes and anti-Stokes Raman spectra of the thiocyanate dimer radical anion, (SCN)2(•-), prepared by pulse radiolysis in water, have been obtained and interpreted in conjunction with theoretical calculations to provide detailed information on the molecular geometry and bond properties of the species. The structural properties of the radical are used to develop a molecular perspective on its thermochemistry in an aqueous solution. Twenty-nine Stokes Raman bands of the radical observed in the 120-4200 cm(-1) region are assigned in terms of the strongly enhanced 220 cm(-1) fundamental, weakly enhanced 721 cm(-1), and moderately enhanced 2073 cm(-1) fundamentals, their overtones, and combinations. Calculations by range-separated hybrid density functionals (ωB97x and LC-ωPBE) support the spectroscopic assignments of the 220 cm(-1) vibration to a predominantly SS stretching mode and the features at 721 cm(-1) and 2073 cm(-1) to CS and CN symmetric stretching modes, respectively. The corresponding bond lengths are 2.705 (±0.036) Å, 1.663 (±0.001) Å, and 1.158 (±0.002) Å. A first order anharmonicity of 1 cm(-1) determined for the SS stretching mode suggests a convergence of vibrational states at an energy of ∼1.5 eV, using the Birge-Sponer extrapolation. This value, estimated for the radical confined in solvent cage, compares well with the calculated gas-phase energy of 1.26 ± 0.04 eV required for the radical to dissociate into SCN(•) and SCN(-) fragments. The enthalpy of dissociation drops to 0.60 ± 0.03 eV in water when solvent dielectric effects on the radical and its dissociation products upon S-S bond scission are incorporated in the calculations. No frequency shift or spectral broadening was observed between light and heavy water solvents, indicating that the motion of solvent molecules in the hydration shell has no perceptible effect on the intramolecular dynamics of the radical. The Stokes and anti-Stokes Raman

  8. Study of radicals, clusters and transition state species by anion photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Arnold, Don Wesley [Univ. of California, Berkeley, CA (United States)

    1994-08-01

    Free radicals, elemental and van der Waals clusters and transition state species for bimolecular chemical reactions are investigated using anion photoelectron spectroscopy. Several low-lying electronic states of ozone have been identified via photoelectron spectroscopy of O3-. A characterization of these states is important to models for atmospheric ozone reaction kinetics. The fluoroformyloxyl radical, FCO2, has been investigated, providing vibrational frequencies and energies for two electronic states. The technique has also been employed to make the first direct observation and characterization of the NNO2 molecule. Several electronic states are observed for this species which is believed to play a role as a reactive intermediate in the N + NO2 reaction. The experimental results for all three of these radicals are supplemented by ab initio investigations of their molecular properties. The clusters investigations include studies of elemental carbon clusters (C2- - C11-), and van der Waals clusters (X-(CO2)n, X = I, Br, Cl; n {le} 13 and I- (N2O)n=1--11). Primarily linear clusters are observed for the smaller carbon clusters, while the spectra of the larger clusters contain contribution from cyclic anion photodetachment. Very interesting ion-solvent interactions are observed in the X-(CO2)n clusters. The transition state regions for several bimolecular chemical reactions have also been investigated by photodetachment of a negative ion precursor possessing a geometry similar to that of the transition state species. These spectra show features which are assigned to motions of the unstable neutral complex existing between reactants and products.

  9. A potentiometric study of molecular heteroconjugation equilibria in (n-butylamine+acetic acid) systems in binary (acetonitrile +1,4-dioxane) solvent mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Czaja, Malgorzata [Department of General Chemistry, University of Gdansk, Sobieskiego 18, 80-952 Gdansk (Poland); Makowski, Mariusz [Department of General Chemistry, University of Gdansk, Sobieskiego 18, 80-952 Gdansk (Poland); Chmurzynski, Lech [Department of General Chemistry, University of Gdansk, Sobieskiego 18, 80-952 Gdansk (Poland)]. E-mail: lech@chem.univ.gda.pl

    2006-05-15

    By using the potentiometric method the following quantities have been determined: acidity constants of molecular acid, K{sub a}(HA), of cationic acid, K{sub a}(BH{sup +}), anionic and cationic homoconjugation constants, K{sub AHA{sup -}} and K{sub BHB{sup +}}, respectively, as well as molecular heteroconjugation constants, K{sub AHB}, in (n-butylamine+acetic acid) systems without proton transfer in binary (acetonitrile+1,4-dioxane), AN+D, solvent mixtures. The results of these measurements have shown that the magnitudes of the molecular heteroconjugation constants do not depend on the 1,4-dioxane content in the mixed solvent, i.e., on solvent polarity. It has also been found that in the (acid+base) systems without proton transfer, the manner of carrying out the titration (direct B+HA vs. reverse HA+B) does not affect the magnitudes of the molecular heteroconjugation constants.

  10. Potentiometric investigations of (acid+base) equilibria in (n-butylamine+acetic acid) systems in binary (acetone+cyclohexane) solvent mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Czaja, MaIgorzata [Department of General Chemistry, University of Gdansk, Sobieskiego 18, 80-952 Gdansk (Poland); Kozak, Anna [Department of General Chemistry, University of Gdansk, Sobieskiego 18, 80-952 Gdansk (Poland); Makowski, Mariusz [Department of General Chemistry, University of Gdansk, Sobieskiego 18, 80-952 Gdansk (Poland); Chmurzynski, Lech [Department of General Chemistry, University of Gdansk, Sobieskiego 18, 80-952 Gdansk (Poland)]. E-mail: lech@chem.univ.gda.pl

    2005-08-15

    By using the potentiometric titration method, standard equilibrium constants have been determined of acid dissociation of molecular acid, K{sub a}(HA), cationic acid, K{sub a}(BH{sup +}), of anionic and cationic homoconjugation, K{sub AHA{sup -}}andK{sub BHB{sup +}}, respectively, and of molecular heteroconjugation, K{sub AHB} (K{sub BHA}), in (acid+base) systems without proton transfer consisting of n-butylamine and acetic acid in binary (acetone+cyclohexane) solvent mixtures. The results have shown that both the pK{sub a}(HA) and pK{sub a}(BH{sup +}), as well as lgK{sub AHA{sup -}} values change non-linearly as a function of composition of the solvent mixture. On the other hand, standard molecular heteroconjugation constants without proton transfer do not depend on the cyclohexane content in the mixture, i.e. on solvent polarity.

  11. Solvent-Controlled Assembly of ionic Metal-Organic Frameworks Based on Indium and Tetracarboxylate Ligand: Topology Variety and Gas Sorption Properties

    KAUST Repository

    Zheng, Bing

    2016-07-15

    Four Metal-Organic Frameworks (MOFs) based on Indium and tetracarboxylate ligand have been synthesized through regulation of the solvent conditions, the resulted compounds not only exhibited rich structural topologies (pts, soc and unique topologies), but also interesting charge reversal framework features. By regulating the solvent, different building units (indium monomer, trimer) have been generated in situ, and they are connected with the ligand to form ionic frameworks 1-4, respectively. Among the synthesized four ionic frameworks, compounds 3 and 4 could keep their crystallinity upon heating temperature up to 300oC after fully removal of solvent guest molecules, they also exhibit the charge reversal framework features (3 adopts an overall cationic framework, while 4 has an anionic framework). Both compounds 3 and 4 exhibit significant uptake capacity for CO2 and H2, besides that, compounds 3 and 4 also present excellent selective adsorption of CO2 over N2 and CH4.

  12. New Polymeric Membranes for Organic Solvent Nanofiltration

    KAUST Repository

    Aburabie, Jamaliah

    2017-05-01

    The focus of this dissertation was the development, synthesis and modification of polymers for the preparation of membranes for organic solvent nanofiltration. High chemical stability in a wide range of solvents was a key requirement. Membranes prepared from synthesized polymers as well as from commercial polymers were designed and chemically modified to reach OSN requirements. A solvent stable thin-film composite (TFC) membrane is reported, which is fabricated on crosslinked polythiosemicarbazide (PTSC) as substrate. The membranes exhibited high fluxes towards solvents like THF, DMF and DMSO ranging around 20 L/m2 h at 5 bar with a MWCO of around 1000 g/mol. Ultrafiltration PTSC membranes were prepared by non-solvent induced phase separation and crosslinked with GPTMS. The crosslinking reaction was responsible for the formation of an inorganic-type-network that tuned the membrane pore size. The crosslinked membranes acquired high solvent stability in DMSO, DMF and THF with a MWCO above 1300 g/mol. Reaction Induced Phase Separation (RIPS) was introduced as a new method for the preparation of skinned asymmetric membranes. These membranes have two distinctive layers with different morphologies both from the same polymer. The top dense layer is composed of chemically crosslinked polymer chains while the bottom layer is a porous structure formed by non-crosslinked polymer chains. Such membranes were tested for vitamin B12 in solvents after either crosslinking the support or dissolving the support and fixing the freestanding membrane on alumina. Pebax® 1657 was utilized for the preparation of composite membranes by simple coating. Porous PAN membranes were coated with Pebax® 1657 which was then crosslinked using TDI. Crosslinked Pebax® membranes show high stability towards ethanol, propanol and acetone. The membranes were also stable in DMF once crosslinked PAN supports were used. Sodium alginate polymer was investigated for the preparation of thin film composite

  13. Chlorinated solvent replacements recycle/recovery review report

    Energy Technology Data Exchange (ETDEWEB)

    Beal, M.; Hsu, D.; McAtee, R.E.; Weidner, J.R. [EG and G Idaho, Inc., Idaho Falls, ID (United States); Berg, L.; McCandless, F.P.; Waltari, S.; Peterson, C. [Montana State Univ., Bozeman, MT (United States). Dept. of Chemical Engineering

    1992-08-01

    This report is a literature review of waste solvents recycle/recovery methods and shows the results of solvent separations using membrane and distillation technologies. The experimental solvent recovery methods were conducted on solvent replacements for chlorinated solvents at Montana State University. The literature review covers waste solvents separation using distillation, membranes decantation, filtration, carbon adsorption, solvent extraction, and other vapor-phase separation techniques. The results of this study identify solvent distillation methods as the most common separation technique. The alternative separation methods typically supplement distillation. The study shows the need for industries to identify waste solvent disposal methods and investigate the economics of waste solvent recycling as a possible waste reduction method.

  14. Solvent/non-solvent sintering: a novel route to create porous microsphere scaffolds for tissue regeneration.

    Science.gov (United States)

    Brown, Justin L; Nair, Lakshmi S; Laurencin, Cato T

    2008-08-01

    Solvent/non-solvent sintering creates porous polymeric microsphere scaffolds suitable for tissue engineering purposes with control over the resulting porosity, average pore diameter, and mechanical properties. Five different biodegradable biocompatible polyphosphazenes exhibiting glass transition temperatures from -8 to 41 degrees C and poly (lactide-co-glycolide), (PLAGA) a degradable polymer used in a number of biomedical settings, were examined to study the versatility of the process and benchmark the process to heat sintering. Parameters such as: solvent/non-solvent sintering solution composition and submersion time effect the sintering process. PLAGA microsphere scaffolds fabricated with solvent/non-solvent sintering exhibited an interconnected porosity and pore size of 31.9% and 179.1 mum, respectively which was analogous to that of conventional heat sintered PLAGA microsphere scaffolds. Biodegradable polyphosphazene microsphere scaffolds exhibited a maximum interconnected porosity of 37.6% and a maximum compressive modulus of 94.3 MPa. Solvent/non-solvent sintering is an effective strategy for sintering polymeric microspheres, with a broad spectrum of glass transition temperatures, under ambient conditions making it an excellent fabrication route for developing tissue engineering scaffolds and drug delivery vehicles. (c) 2007 Wiley Periodicals, Inc.

  15. Tracking Solvent Uptake in Block Polymer Thin Films during Solvent Vapor Annealing

    Science.gov (United States)

    Shelton, Cameron; Jones, Ronald; Dura, Joseph; Epps, Thomas

    2015-03-01

    A key goal in the block polymer (BP) thin films community is the design of a template-free, universal annealing method to control nanoscale self-assembly over large length scales. Solvent vapor annealing (SVA) offers a unique solution to this challenge with its ability to tune substrate surface, free surface, and polymer-polymer interactions by exposing films to appropriate solvents. However, there is little understanding of how the solvent behaves during the SVA process. In this work, we utilized the combination of deuterated solvents with small-angle neutron scattering (SANS) and neutron reflectometry to track solvent uptake in poly(styrene-b-isoprene-b-styrene) thin films. Two solvents were chosen for this analysis: d-hexane (isoprene selective) and d-benzene (styrene selective). Our work has shown that solvent choice and partial pressure have a significant impact on how solvent segregates within individual polymer domains and the film as a whole, directly impacting the restructuring of polymer domains. This work provides further understanding of the mechanism behind SVA, thereby making it easier to select appropriate conditions for desired self-assembly control.

  16. Study of the interactions between poly(ethylene oxide) and anionic surfactants in elongational flow

    Science.gov (United States)

    Smitter, Luis Manuel

    2001-07-01

    The rheology of polymer solutions is important in a wide variety of applications. In particular, solutions of high-molecular-weight, flexible polymers exhibit an increase in their apparent extensional viscosity with strain rate under extensional flow conditions. This extension thickening is due to formation of transient entanglements of polymer molecules. Certain commercial fluids contain both polymers and surfactants that might interact at the molecular level. These interactions affect the conformation of the polymer chain and, therefore, the rheological behavior of the solution. For instance, addition of anionic surfactants to solutions of nonionic polymers is known to induce increases in the shear viscosity of aqueous solution. This work investigates the behavior of aqueous solutions of a high-molecular-weight poly(ethylene oxide) (PEO), a nonionic, flexible polymer, and the anionic surfactants sodium dodecyl sulfate (SDS), sodium dodecyl benzene sulfonate (SDBS) and a commercial alpha-olefin sulfonate (AOS) in extensional flows. The extensional rheology of polymer/surfactant solutions is studied in an opposed-jets device, which generates a flow field close to uniaxial extension. For PEO/SDS mixtures, the results show that formation of micellar aggregates of SDS along the PEO chains results in an increase in the strength of extension thickening of PEO solutions by promoting intermolecular interactions between polymer chains. The minimum PEO concentration required to form intermolecular entanglements is substantially reduced in the presence of micellar aggregates. In solutions containing NaCl, intramolecular interactions are observed at low PEO concentrations. These reduce the strength of extension thickening. Addition of a co-solvent is investigated. The presence of alcohols in the aqueous solutions affects their rheology by changing the solvent nature for both PEO and SDS. In particular, n-octanol promotes aggregation of SDS along the PEO chains, enhancing

  17. Assessment of solvents for cellulose dissolution.

    Science.gov (United States)

    Ghasemi, Mohammad; Tsianou, Marina; Alexandridis, Paschalis

    2017-03-01

    A necessary step in the processing of biomass is the pretreatment and dissolution of cellulose. A good solvent for cellulose involves high diffusivity, aggressiveness in decrystallization, and capability of disassociating the cellulose chains. However, it is not clear which of these factors and under what conditions should be improved in order to obtain a more effective solvent. To this end, a newly-developed phenomenological model has been applied to assess the controlling mechanism of cellulose dissolution. Among the findings, the cellulose fibers remain crystalline almost to the end of the dissolution process for decrystallization-controlled kinetics. In such solvents, decreasing the fiber crystallinity, e.g., via pretreatment, would result in a considerable increase in the dissolution rate. Such insights improve the understanding of cellulose dissolution and facilitate the selection of more efficient solvents and processing conditions for biomass. Specific examples of solvents are provided where dissolution is limited due to decrystallization or disentanglement. Copyright © 2016 Elsevier Ltd. All rights reserved.

  18. Ions, solutes and solvents, oh my!

    Energy Technology Data Exchange (ETDEWEB)

    Kemp, Daniel David [Iowa State Univ., Ames, IA (United States)

    2009-08-01

    Modern methods in ab initio quantum mechanics have become efficient and accurate enough to study many gas-phase systems. However, chemists often work in the solution phase. The presence of solvent molecules has been shown to affect reaction mechanisms1, lower reaction energy barriers2, participate in energy transfer with the solute3 and change the physical properties of the solute4. These effects would be overlooked in simple gas phase calculations. Careful study of specific solvents and solutes must be done in order to fully understand the chemistry of the solution phase. Water is a key solvent in chemical and biological applications. The properties of an individual water molecule (a monomer) and the behavior of thousands of molecules (bulk solution) are well known for many solvents. Much is also understood about aqueous microsolvation (small clusters containing ten water molecules or fewer) and the solvation characteristics when bulk water is chosen to solvate a solute. However, much less is known about how these properties behave as the cluster size transitions from the microsolvated cluster size to the bulk. This thesis will focus on species solvated with water clusters that are large enough to exhibit the properties of the bulk but small enough to consist of fewer than one hundred solvent molecules. New methods to study such systems will also be presented.

  19. Ion and solvent transfers and trapping phenomena during n-doping of PEDOT films

    Energy Technology Data Exchange (ETDEWEB)

    Hillman, A. Robert [Department of Chemistry, University of Leicester, Leicester LE1 7RH (United Kingdom)], E-mail: arh7@le.ac.uk; Daisley, Samantha J. [Department of Chemistry, University of Leicester, Leicester LE1 7RH (United Kingdom); Bruckenstein, Stanley [Department of Chemistry, University at Buffalo, SUNY, Buffalo, NY 14260 (United States)

    2008-04-20

    Electrochemical quartz crystal microbalance (EQCM) measurements were made during the n-doping of PEDOT films exposed to a range of electrolytes (TEABF{sub 4}, TPABF{sub 4} and TEATos) in CH{sub 3}CN solvent. The films were acoustically thin ('rigid'), so that the EQCM response could be interpreted gravimetrically. Correlation of the current with the time differential of the mass response allowed the determination of dopant ion and solvent fluxes as functions of applied potential during cyclic voltammetric experiments. This interpretation required the use of Faraday's law, the electroneutrality condition and the assumption (supported by variation of co-ion) that the film is permselective. The ion and solvent fluxes are in opposing directions for TEA{sup +} insertion, but in the same direction for TPA{sup +} insertion. As a result, the net mass change is much smaller in TEABF{sub 4} electrolyte. In both the doping or undoping half-cycles, the ion and solvent fluxes normalise with potential scan rate, indicating that they are not subject to kinetic or transport limitations on the moderate time scale of the experiment. However, there is considerable hysteresis between the responses in the two scan directions, indicating the presence of slow polymer-based processes. When the potential limits are extended to encompass p- and n-doping regimes sequentially, additional response components on the rising edges of the two doping processes signal the participation of 'trapping' phenomena. The amounts of trapped dopant charge are independent of potential scan rate for both p- and n-doping. The fraction of injected charge that is trapped is larger by an order of magnitude for cation, but the absolute amounts of trapped ion are similar for cation and anion.

  20. Recommended methods for purification of solvents and tests for impurities

    CERN Document Server

    Coetzee, J F

    1982-01-01

    Recommended Methods for Purification of Solvents and Tests for Impurities is a compilation of recommended procedures for purification of solvents and tests for solvent impurities. Ten solvents are covered: acetonitrile, sulfolane, propylene carbonate, dimethyl sulfoxide, dimethylformamide, hexamethylphosphoramide, pyridine, ethylenediamine, N-methylacetamide, and N-methylpropionamide. This book is comprised of 12 chapters and opens with an introduction to general aspects of impurity effects. The rationale for the selection of solvent is explained, and the relative reactivities of solutes in di

  1. Treatment of acute non-anion gap metabolic acidosis

    Science.gov (United States)

    Kraut, Jeffrey A.; Kurtz, Ira

    2015-01-01

    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. PMID:25852932

  2. 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)

  3. 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 < 0.05) but sodium alginate only in concentrations <0.1% increased drug permeability. It is concluded that the anionic 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.

  4. Cellular uptake mechanisms of novel anionic siRNA lipoplexes.

    Science.gov (United States)

    Kapoor, Mamta; Burgess, Diane J

    2013-04-01

    To investigate cellular uptake pathways of novel anionic siRNA-lipoplexes as a function of formulation composition. Anionic formulations with anionic lipid/Ca(2+)/siRNA ratio of 1.3/2.5/1 (AF1) and 1.3/0.3/1 (AF2) were utilized. Uptake mechanisms were investigated using uptake inhibition and co-localization approaches in breast cancer cells. Actin-mediated uptake was investigated using actin polymerization and rearrangement assays. Silencing efficiency and endosomal escaping capability of lipoplexes were evaluated. The cationic formulation Lipofectamine-2000 was used as a control. Anionic lipoplexes entered the breast cancer cells via endocytosis specifically via macropinocytosis or via both macropinocytosis and HSPG (heparin sulfate proteoglycans) pathways, depending on the Ca(2+)/siRNA ratio. Additionally, uptake of these lipoplexes was both microtubule and actin dependent. The control cationic lipid-siRNA complexes (Lipofectamine-2000) were internalized via both endocytic (phagocytosis, HSPG) and non-endocytic (membrane fusion) pathways. Their uptake was microtubule independent but actin dependent. Silencing efficiency of the AF2 formulation was negligible mainly due to poor endosomal release (rate-limiting step). Formulation composition significantly influences the internalization mechanism of anionic lipoplexes. Uptake mechanism together with formulation bioactivity helped in identification of the rate-limiting steps to efficient siRNA delivery. Such studies are extremely useful for formulation optimization to achieve enhanced intracellular delivery of nucleic acids.

  5. 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.

  6. Ion aggregation in concentrated aqueous and methanol solutions of polyoxometallates Keggin anions: the effect of counterions investigated by molecular dynamics simulations.

    Science.gov (United States)

    Chaumont, Alain; Wipff, Georges

    2008-12-14

    Aqueous solutions of the polyoxometallate alpha-PW(12)O(40)(3-) Keggin anion "PW(3-)" have been simulated by molecular dynamics, comparing two anion concentrations (0.06 and ca. 0.15 mol l(-1)) and Cs(+), NBu(4)(+), UO(2)(2+), Eu(3+), H(3)O(+) and H(5)O(2)(+) as neutralizing M(n+) counterions. They reveal marked counterion effects of the degree of salt dilution, cation-anion and anion-anion relationships. The hydrophobic NBu(4)(+) cations tend to surround PW(3-)'s via loose contacts, leading to "phase separation" between water and a humid salty domain, overall neutral, where all ions are concentrated. The other studied cations are more hydrophilic and generally separated from the PW(3-) anions. The most important finding concerns the aggregation of PW's, mostly as dimers with short contacts (PP < 12 A), but also as higher (PW(3-))(n) oligomers (n = 3 to 5) in concentrated solutions where the proportion of the aggregates ranges from ca. 9 to 46%, depending on the counterion. While Eu(3+) and UO(2)(2+) are fully hydrated and interact at short distances with PWs as solvent-separated ion pairs, Cs(+) can form contact ion pairs, as well as solvent-separated ions. Among the mono-charged counterions, H(5)O(2)(+) gives highest aggregation (ca. 47%, involving 32% of dimers, 11% of trimers and 3% of tetramers), pointing to the influence of the proton state (H(5)O(2)(+)vs. H(3)O(+)) on PW's aggregation and condensation. The dynamic properties are also dependent on M(n+): the PW's diffusion coefficients are lowest with NBu(4)(+), and highest for Cs(+), thus reflecting the degree of ion condensation in water. The role of water on the solution state of the PW salts is further demonstrated by simulating the most concentrated systems in methanol solution. Because MeOH solvates less well the M(n+) cation than does H(2)O and cannot afford bridging relays between PW's, one finds a higher proportion of PW(3-)M(n+) contacts, and no (PW(3-))(n) oligomers with short contacts in methanol.

  7. Selection of optimum ionic liquid solvents for flavonoid and phenolic acids extraction

    Science.gov (United States)

    Rahman, N. R. A.; Yunus, N. A.; Mustaffa, A. A.

    2017-06-01

    Phytochemicals are important in improving human health with their functions as antioxidants, antimicrobials and anticancer agents. However, the quality of phytochemicals extract relies on the efficiency of extraction process. Ionic liquids (ILs) have become a research phenomenal as extraction solvent due to their unique properties such as unlimited range of ILs, non-volatile, strongly solvating and may become either polarity. In phytochemical extraction, the determination of the best solvent that can extract highest yield of solute (phytochemical) is very important. Therefore, this study is conducted to determine the best IL solvent to extract flavonoids and phenolic acids through a property prediction modeling approach. ILs were selected from the imidazolium-based anion for alkyl chains ranging from ethyl > octyl and cations consisting of Br, Cl, [PF6], BF4], [H2PO4], [SO4], [CF3SO3], [TF2N] and [HSO4]. This work are divided into several stages. In Stage 1, a Microsoft Excel-based database containing available solubility parameter values of phytochemicals and ILs including its prediction models and their parameters has been established. The database also includes available solubility data of phytochemicals in IL, and activity coefficient models, for solid-liquid phase equilibrium (SLE) calculations. In Stage 2, the solubility parameter values of the flavonoids (e.g. kaempferol, quercetin and myricetin) and phenolic acids (e.g. gallic acid and caffeic acid) are determined either directly from database or predicted using Stefanis and Marrero-Gani group contribution model for the phytochemicals. A cation-anion contribution model is used for IL. In Stage 3, the amount of phytochemicals extracted can be determined by using SLE relationship involving UNIFAC-IL model. For missing parameters (UNIFAC-IL), they are regressed using available solubility data. Finally, in Stage 4, the solvent candidates are ranked and five ILs, ([OMIM] [TF2N], [HeMIM] [TF2N], [HMIM] [TF2N

  8. Effect of Solvents on the Behavior of Lithium and Superoxide Ions in Lithium-Oxygen Battery Electrolytes.

    Science.gov (United States)

    Smirnov, Vladimir S; Kislenko, Sergey A

    2017-11-09

    The molecular life of intermediates, namely, O2- and Li+ , produced during the discharge of aprotic Li-O2 batteries was investigated by molecular dynamics simulation. This work is of potential interest in the development of new electrolytes for Li-air batteries. We present the results on the structure and stability of the Li+ and O2- solvation shells and the thermodynamics and kinetics of the ion-association reaction in solvents such as dimethyl sulfoxide (DMSO), dimethoxyethane (DME), and acetonitrile (ACN). The residence time of solvent molecules in the Li+ solvation shell increases with the solvent donor number and is 100 times larger in DMSO than in ACN. In DMSO and DME, the Li+ ion diffuses with its solvation shell as a whole. On the contrary, in ACN it diffuses as a "bare" ion because of weak solvation. The rate constant for the association of the lithium ion with the superoxide anion in DMSO is two orders of magnitude slower than that in ACN due to fact that the free-energy barrier is 2.5 times larger in DMSO than in ACN. In addition, we show that despite the strong dependence of the Li+ shell stability on donor number, the rate of association does not necessarily correlate with this solvent property. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Hazardous Solvent Substitution Data System tutorial

    Energy Technology Data Exchange (ETDEWEB)

    Twitchell, K.E.; Skinner, N.L.

    1993-07-01

    This manual is the tutorial for the Hazardous Solvent Substitution Data System (HSSDS), an online, comprehensive system of information on alternatives to hazardous solvents and related subjects. The HSSDS data base contains product information, material safety data sheets, toxicity reports, usage reports, biodegradable data, product chemical element lists, and background information on solvents. HSSDS use TOPIC{reg_sign} to search for information based on a query defined by the user. TOPIC provides a full text retrieval of unstructured source documents. In this tutorial, a series of lessons is provided that guides the user through basic steps common to most queries performed with HSSDS. Instructions are provided for both window-based and character-based applications.

  10. [Remaining solvents in dry cleaned over clothes].

    Science.gov (United States)

    Tashiro, H; Fujishiro, K; Matsuno, K; Kawamoto, T; Okubo, T

    1999-03-01

    We examined remaining solvents in dry cleaned trousers to estimate the magnitude of environmental pollution. A cleaning solvent of petroleum hydrocarbon was analyzed by means of capillary column mass spectrum gas chromatography. Principal ingredients were identified to be nonane, decane and undecane. The same main components were detected in dry cleaned trousers. Total amounts of evaporated vapor from a pair of trousers (480 g) in 5 days after dry cleaning were nonane (0.73 mg), decane (1.53 mg) and undecane (1.09 mg). The levels on the fifth day were 5%(nonane), 18%(decane) and 32%(undecane) of the first day's concentration, respectively. The half times of the remaining solvents were 1.0 day (nonane), 1.7 days (decane) and 2.7 days (undecane), respectively.

  11. Alternative Solvents through Green Chemistry Project

    Science.gov (United States)

    Hintze, Paul E.; Quinn, Jacqueline

    2014-01-01

    Components in the aerospace industry must perform with accuracy and precision under extreme conditions, and surface contamination can be detrimental to the desired performance, especially in cases when the components come into contact with strong oxidizers such as liquid oxygen. Therefore, precision cleaning is an important part of a components preparation prior to utilization in aerospace applications. Current cleaning technologies employ a variety of cleaning agents, many of which are halogenated solvents that are either toxic or cause environmental damage. Thus, this project seeks to identify alternative precision cleaning solvents and technologies, including use of less harmful cleaning solvents, ultrasonic and megasonic agitation, low-pressure plasma cleaning techniques, and supercritical carbon dioxide extraction. Please review all data content found in the Public Data tab located at: https:techport.nasa.govview11697public

  12. Solvent-dependent excited-state hydrogen transfer and intersystem crossing in 2-(2′-hydroxyphenyl)-benzothiazole

    KAUST Repository

    Aly, Shawkat Mohammede

    2015-02-12

    The excited-state intramolecular hydrogen transfer (ESIHT) of 2-(2′-hydroxyphenyl) benzothiazole (HBT) has been investigated in a series of nonpolar, polar aprotic, and polar protic solvents. A variety of state-of-the-art experimental methods were employed, including femto- and nanosecond transient absorption and fluorescence upconversion spectroscopy with broadband capabilities. We show that the dynamics and mechanism of ESIHT of the singlet excited HBT are strongly solvent-dependent. In nonpolar solvents, the data demonstrate that HBT molecules adopt a closed form stabilized by O-H⋯N chelated hydrogen bonds with no twisting angle, and the photoinduced H transfer occurs within 120 fs, leading to the formation of a keto tautomer. In polar solvents, owing to dipole-dipole cross talk and hydrogen bonding interactions, the H transfer process is followed by ultrafast nonradiative deactivation channels, including ultrafast internal conversion (IC) and intersystem crossing (ISC). This is likely to be driven by the twisting motion around the C-C bond between the hydroxyphenyl and thiazole moieties, facilitating the IC back to the enol ground state or to the keto triplet state. In addition, our femtosecond time-resolved fluorescence experiments indicate, for the first time, that the lifetime of the enol form in ACN is approximately 280 fs. This observation indicates that the solvent plays a crucial role in breaking the H bond and deactivating the excited state of the HBT. Interestingly, the broadband transient absorption and fluorescence up-conversion data clearly demonstrate that the intermolecular proton transfer from the excited HBT to the DMSO solvent is about 190 fs, forming the HBT anion excited state.

  13. Deuterium isotope effects on the interaction between hyperbranched polyethylene imine and an anionic surfactant.

    Science.gov (United States)

    Bastardo, L A; Mészaros, R; Varga, I; Gilanyi, T; Cleasson, P M

    2005-08-25

    Solvent isotope effects on the interaction between the hyperbranched cationic polyelectrolyte, polyethylene imine (PEI), and the anionic surfactant sodium dodecyl sulfate (SDS) were investigated using potentiometric titration and eletrophoretic mobility measurements. In the basic pH range, a significantly higher fraction of the amine groups was found to be protonated when the PEI was dissolved in D2O compared to H2O at the same pH/pD. The difference in polymer charge in the two solvents decreases gradually with decreasing pH, and it completely diminishes at around pH = 4. Electrophoretic mobility measurements of PEI/SDS complexes at different pH values correlated very well with these observations. At pH/pD approximately 9 a much higher mobility of the PEI/SDS complexes was found in D2O than in H2O at low surfactant concentrations, and the charge neutralization point shifted to a considerably larger surfactant concentration in heavy water. These results can be explained by the significantly higher charge density of the PEI in D2O compared to H2O. However, at the natural pH/pD as well as at pH = 4 and pD = 4 conditions the PEI molecules have roughly equal charge densities, which result in very similar charged characteristics (mobilities) of the PEI/SDS complexes as well as the same charge neutralization SDS concentration. It can be concluded that extreme care must be taken in the general analysis of those experiments in which weak polyelectrolyte/surfactant aggregates are investigated in heavy water, and then these observations are correlated with structures of the same system in water.

  14. High mobility half-metallicity in the (LaMnO3)2/(SrTiO3)8 superlattice

    Science.gov (United States)

    Cossu, F.; Singh, N.; Schwingenschlögl, U.

    2013-01-01

    First principles calculations have been performed to investigate the LaMnO3/SrTiO3 superlattice. Structural relaxation within the generalized gradient approximation results in no significant tiltings or rotations of oxygen octahedra, but in distinct distortions in the SrTiO3 region. Taking into account the onsite Coulomb interaction, we find that the Mn spins order ferromagnetically, in contrast to the antiferromagnetic state of bulk LaMnO3. Most importantly, the interface strain combined with charge transfer across the interface induces half-metallicity within the MnO2 layers. The superlattice is particulary interesting for spintronics applications because the half-metallic states are characterized by an extraordinary high mobility.

  15. Glycyrrhizin inhibits porcine epidemic diarrhea virus infection and attenuates the proinflammatory responses by inhibition of high mobility group box-1 protein.

    Science.gov (United States)

    Huan, Chang-Chao; Wang, Hua-Xia; Sheng, Xiang-Xiang; Wang, Rui; Wang, Xin; Mao, Xiang

    2017-06-01

    Porcine epidemic diarrhea (PED), caused by porcine epidemic diarrhea virus (PEDV) infection, leads to significant economic losses in the swine industry worldwide. In our studies, we found that glycyrrhizin, the major component of licorice root extracts, could moderately inhibit PEDV infection in Vero cells, when analyzed by western blot, qRT-PCR and a plaque formation assay. We also revealed that glycyrrhizin inhibited the entry and replication of PEDV. In addition, we demonstrated that glycyrrhizin decreased the mRNA levels of proinflammatory cytokines. Since glycyrrhizin is a competitive inhibitor of high mobility group box-1 (HMGB1), we confirmed that TLR4 and RAGE (£ associated with PEDV pathogenesis during the infection in Vero cells. In summary, our studies provide a molecular basis for developing novel therapeutic methods to control PEDV infection, based on glycyrrhizin and its derivatives.

  16. 2k{sub F}-selected conductance oscillations of high-mobility two-dimensional electron gas in Corbino devices

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Xiaoxue [International Center for Quantum Materials, School of Physics, Peking University, 100871, Beijing (China); Collaborative Innovation Center of Quantum Matter, 100871, Beijing (China); Zhu, Yuying; Yang, Changli; Lu, Li [Collaborative Innovation Center of Quantum Matter, 100871, Beijing (China); Institute of Physics, Chinese Academy of Sciences, 100190, Beijing (China); Du, Lingjie [Rice University, Houston, Texas 77251-1892 (United States); Pfeiffer, Loren; West, Kenneth [Princeton University, Princeton, New Jersey 08544 (United States); Du, Rui-Rui [International Center for Quantum Materials, School of Physics, Peking University, 100871, Beijing (China); Collaborative Innovation Center of Quantum Matter, 100871, Beijing (China); Rice University, Houston, Texas 77251-1892 (United States)

    2014-11-03

    We have observed electrical-field induced magneto-conductivity oscillations measured in Corbino samples made of a GaAs high-mobility two-dimensional electron gas, and found a consistent interpretation based on a semiclassical model of 2k{sub F}-selected orbital transitions between N and N + 1, 2, 3,…, Landau levels at respective local potentials, where k{sub F} is the Fermi wavevector. From the oscillation period, we deduce an effective mass value, which is consistent with the bare electron band mass of GaAs. In the same devices but with a vanishing electrical field and at elevated temperatures, we observed additional oscillation features, which can be attributed to cyclotron resonance by population of acoustic phonons. We thus demonstrate a method to determine the carrier effective mass and the sound velocity of host crystals by standard electrical transport.

  17. Terahertz tunable detection in self-switching diodes based on high mobility semiconductors: InGaAs, InAs and InSb

    Energy Technology Data Exchange (ETDEWEB)

    Iniguez-de-la-Torre, I; Rodilla, H; Mateos, J; Pardo, D; Gonzalez, T [Departamento de Fisica Aplicada, Universidad de Salamanca, Plaza de la Merced s/n, 37008 Salamanca (Spain); Song, A M, E-mail: indy@usal.e [School of Electrical and Electronic Engineering, University of Manchester, Manchester M60 1QD (United Kingdom)

    2009-11-15

    In this work we report on the use of high mobility materials in the channel of self-switching diodes as potential candidates for terahertz operation. By means of Monte Carlo simulations we envisage the feasibility of tuneable-by-geometry detection in the terahertz range. The low effective mass of InAs and InSb in relation to InGaAs enhances ballistic transport inside the diode, thus improving the amplitude and quality factor of the resonance found in the detection spectra of self-switching diodes. The frequency of the resonant peak is also increased with the use of these narrow band gap semiconductors. The analysis of the noise spectra provides useful information about the origin of the resonance. By decreasing temperature below 300 K, a clear improvement in detection sensitivity is also achieved.

  18. High mobility half-metallicity in the (LaMnO3)2/(SrTiO3)8 superlattice

    KAUST Repository

    Cossu, Fabrizio

    2013-01-28

    First principles calculations have been performed to investigate the LaMnO3/SrTiO3 superlattice. Structural relaxation within the generalized gradient approximation results in no significant tiltings or rotations of oxygen octahedra, but in distinct distortions in the SrTiO3 region. Taking into account the onsite Coulomb interaction, we find that the Mn spins order ferromagnetically, in contrast to the antiferromagnetic state of bulk LaMnO3. Most importantly, the interface strain combined with charge transfer across the interface induces half-metallicity within the MnO2 layers. The superlattice is particulary interesting for spintronics applications because the half-metallic states are characterized by an extraordinary high mobility.

  19. High operational and environmental stability of high-mobility conjugated polymer field-effect transistors through the use of molecular additives

    KAUST Repository

    Nikolka, Mark

    2016-12-12

    Due to their low-temperature processing properties and inherent mechanical flexibility, conjugated polymer field-effect transistors (FETs) are promising candidates for enabling flexible electronic circuits and displays. Much progress has been made on materials performance; however, there remain significant concerns about operational and environmental stability, particularly in the context of applications that require a very high level of threshold voltage stability, such as active-matrix addressing of organic light-emitting diode displays. Here, we investigate the physical mechanisms behind operational and environmental degradation of high-mobility, p-type polymer FETs and demonstrate an effective route to improve device stability. We show that water incorporated in nanometre-sized voids within the polymer microstructure is the key factor in charge trapping and device degradation. By inserting molecular additives that displace water from these voids, it is possible to increase the stability as well as uniformity to a high level sufficient for demanding industrial applications.

  20. Solvent-resistant microporous polymide membranes

    Science.gov (United States)

    Miller, Warren K.; McCray, Scott B.; Friesen, Dwayne T.

    1998-01-01

    An asymmetric microporous membrane with exceptional solvent resistance and highly desirable permeability is disclosed. The membrane is made by a solution-casting or solution-spinning process from a copolyamic acid comprising the condensation reaction product in a solvent of at least three reactants selected from certain diamines and dianhydrides and post-treated to imidize and in some cases cross-link the copolyamic acid. The membrane is useful as an uncoated membrane for ultrafiltration, microfiltration, and membrane contactor applications, or may be used as a support for a permselective coating to form a composite membrane useful in gas separations, reverse osmosis, nanofiltration, pervaporation, or vapor permeation.

  1. Solvent-free fluidic organic dye lasers.

    Science.gov (United States)

    Choi, Eun Young; Mager, Loic; Cham, Tran Thi; Dorkenoo, Kokou D; Fort, Alain; Wu, Jeong Weon; Barsella, Alberto; Ribierre, Jean-Charles

    2013-05-06

    We report on the demonstration of liquid organic dye lasers based on 9-(2-ethylhexyl)carbazole (EHCz), so-called liquid carbazole, doped with green- and red-emitting laser dyes. Both waveguide and Fabry-Perot type microcavity fluidic organic dye lasers were prepared by capillary action under solvent-free conditions. Cascade Förster-type energy transfer processes from liquid carbazole to laser dyes were employed to achieve color-variable amplified spontaneous emission and lasing. Overall, this study provides the first step towards the development of solvent-free fluidic organic semiconducting lasers and demonstrates a new kind of optoelectronic applications for liquid organic semiconductors.

  2. NMR spectroscopy using liquid crystal solvents

    CERN Document Server

    Emsley, JW

    2013-01-01

    NMR Spectroscopy using Liquid Crystal Solvents covers the importance of using a liquid crystal solvent in NMR to derive nuclear dipolar spin-spin coupling constants. This book is composed of ten chapters, and begins with a brief description of the features and benefits of liquid crystal in NMR spectroscopic analysis. The succeeding chapters deal with the mode of operation of nuclear spin Hamiltonian for partially oriented molecules and the analysis of NMR spectra of partially oriented molecules, as well as the determination of rigid molecule structure. These topics are followed by discussions

  3. Kinetics of solvent-swelling of coal

    Energy Technology Data Exchange (ETDEWEB)

    Moreno, G.; Rincon, J.M.; Mora, E. [Lab. de Combustibles, Univ. Nacional de Colombia, Santafe de Bogota (Colombia); Klose, W. [GF Thermodynamik, Kassel Univ. (Germany)

    1997-12-31

    The kinetics of coal swelling by solvent of different basic strength is followed; Cerrejon and Yerbabuena (Colombian coals), Sacer-Endsdorf and Ruhr-Anna (Germany coals) were swollen with tetrahydrofuran, pyridine and butylamine. It was found that the swelling index decreases both with solvent basicity and coal rank. When the coal rank increases, the rates of swelling are: Initially, THF follows Fickian diffusion then follows anomalous case near case II; pyridine follows anomalous case near Fickian diffusion, whereas rate with butylamine initially is anomalous case of transport to Fickian diffusion. (orig.)

  4. Solvent dependence of cyanoindole fluorescence lifetime

    Science.gov (United States)

    Hilaire, Mary Rose; Mukherjee, Debopreeti; Troxler, Thomas; Gai, Feng

    2017-10-01

    Several cyanotryptophans have been shown to be useful biological fluorophores. However, how their fluorescence lifetimes vary with solvent has not been examined. In this regard, herein we measure the fluorescence decay kinetics as well as the absorption and emission spectra of six cyanoindoles in different solvents. In particular, we find, among other results, that only 4-cyanoindole affords a long fluorescence lifetime and hence high quantum yield in H2O. Therefore, our measurements provide not only a guide for choosing which cyanotryptophan to use in practice but also data for computational modeling of the substitution effect on the electronic transitions of indole.

  5. 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.

  6. Differential stabilization of adenine quartets by anions and cations.

    Science.gov (United States)

    van der Wijst, Tushar; Lippert, Bernhard; Swart, Marcel; Guerra, Célia Fonseca; Bickelhaupt, F Matthias

    2010-03-01

    We have investigated the structures and stabilities of four different adenine quartets with alkali and halide ions in the gas phase and in water, using dispersion-corrected density functional theory at the BLYP-D/TZ2P level. First, we examine the empty quartets and how they interact with alkali cations and halide anions with formation of adenine quartet-ion complexes. Second, we examine the interaction in a stack, in which a planar adenine quartet interacts with a cation or anion in the periphery as well as in the center of the quartet. Interestingly, for the latter situation, we find that both cations and anions can stabilize a planar adenine quartet in a stack.

  7. Ion-Pair Oligomerization of Chromogenic Triangulenium Cations with Cyanostar-Modified Anions That Controls Emission in Hierarchical Materials

    DEFF Research Database (Denmark)

    Qiao, Bo; Hirsch, Brandon E.; Lee, Semin

    2017-01-01

    to create these materials is limited. In this work, we extend the salts from small halides to large inorganic anions and determine how the structure coevolves with the emission properties using solution assemblies. We study the chromogenic trioxatriangulenium (TOTA+) cation and its coassembly with cyanostar...... (CS) macrocycles selected to modify tetrafluoroborate (BF4 -) counteranions through formation of 2:1 sandwich complexes. In the solid state, the TOTA+ cation stacks in an alternating manner with the sandwich complexes producing new red-shifted emission and absorption bands. Critical to assigning...... the structural origin of the new optical features across the four levels of organization (1° → 4°) is the selection of specific solvents to produce and characterize different assemblies present in the hierarchical structure. A key species is the electrostatically stabilized ion pair between the TOTA+ cation...

  8. Charge effect on the diffusion coefficient and the bimolecular reaction rate of diiodide anion radical in room temperature ionic liquids.

    Science.gov (United States)

    Nishiyama, Yoshio; Terazima, Masahide; Kimura, Yoshifumi

    2009-04-16

    The diffusion coefficients of diiodide anion radical, I(2)(-), in room temperature ionic liquids (RTILs) were determined by the transient grating (TG) method using the photochemical reaction of iodide. The diffusion coefficients we obtained were larger in RTILs than the theoretical predictions by the Stokes-Einstein relation, whereas both values are similar in conventional solvents. By comparison with the diffusion coefficients of neutral molecules, it was suggested that the Coulomb interaction between I(2)(-) and constituent ions of RTILs strongly affects the diffusion coefficients. The bimolecular reaction rates between I(2)(-) were calculated by the Debye-Smoluchowski equation using the experimentally determined diffusion coefficients. These calculated reaction rate were much smaller than the experimentally determined rates (Takahashi, K.; et al. J. Phys. Chem. B 2007, 111, 4807), indicating the charge screening effect of RTILs.

  9. Anion-macrodipole interactions: self-assembling oligourea/amide macrocycles as anion transporters that respond to membrane polarization.

    Science.gov (United States)

    Hennig, Andreas; Fischer, Lucile; Guichard, Gilles; Matile, Stefan

    2009-11-25

    Macrocyclic urea/amide hybrids are introduced as functional, anion-selective membrane transporters in lipid bilayer membranes. Six derivatives with varying side chains (aliphatic and aromatic) and conformations (parallel and antiparallel carbonyl dipoles) are investigated by fluorescence methods, among which the more active aromatic derivatives were selected for an in-depth study. Strong response of transport activity toward anion exchange and weak response toward cation exchange establish anion selectivity for all macrocycles. "Antiparallel" macrocycles that self-assemble into "antiparallel" nanotubes without macrodipole exhibit Hofmeister selectivity. Parallel macrocycles that self-assemble into parallel nanotubes with strong macrodipole are capable of overcoming the dehydration penalty of the Hofmeister bias. Both systems show additional chloride selectivity. The activity of antiparallel and parallel nanotubes in binary mixtures of bromide/perchlorate and chloride/thiocyanate is over- and underadditive, respectively (positive and negative AMFE). The activity of antiparallel nanotubes decreases rapidly with increasing membrane polarization, whereas parallel nanotubes are inactivated at high and activated by membrane potentials at low concentration. Hill coefficients of parallel nanotubes decrease significantly with membrane polarization, whereas those of antiparallel nanotubes increase slightly. The overall unusual characteristics of parallel nanotubes call for a new transport mechanism, where macrodipole-potential interactions account for voltage sensitivity and anion-macrodipole interactions account for anion selectivity.

  10. Cisplatin prevents high mobility group box 1 release and is protective in a murine model of hepatic ischemia/reperfusion injury.

    Science.gov (United States)

    Cardinal, Jon; Pan, Pinhua; Dhupar, Rajeev; Ross, Mark; Nakao, Atsunori; Lotze, Michael; Billiar, Timothy; Geller, David; Tsung, Allan

    2009-08-01

    The nuclear protein high mobility group box 1 (HMGB1) is an important inflammatory mediator involved in the pathogenesis of liver ischemia/reperfusion (I/R) injury. Strategies aimed at preventing its release from stressed or damaged cells may be beneficial in preventing inflammation after I/R. Cisplatin is a member of the platinating chemotherapeutic agents and can induce DNA lesions that are capable of retaining high mobility group proteins inside the nucleus of cells. In vitro studies in primary cultured rat hepatocytes show that nontoxic concentrations of cisplatin can sequester HMGB1 inside the nucleus of hypoxic cells. Similarly, the in vivo administration of nontoxic doses of cisplatin prevents liver damage associated with a well-established murine model of hepatic I/R as measured by lower circulating serum aminotransferase levels, lower hepatic inflammatory cytokine levels including tumor necrosis factor alpha and interleukin-6, lower inducible NO synthase expression, and fewer I/R-associated histopathologic changes. The mechanism of action in vivo appears to involve the capacity of cisplatin to prevent the I/R-induced release of HMGB1 as well as to alter cell survival and stress signaling in the form of autophagy and mitogen-activated protein kinase activation, respectively. Low, nontoxic doses of cisplatin can sequester HMGB1 inside the nucleus of redox-stressed hepatocytes in vitro and prevent its release in vivo in a murine model of hepatic I/R. Furthermore, cell survival and stress signaling pathways are altered by low-dose cisplatin. Therefore, platinating agents may provide a novel approach to mitigating the deleterious effects of I/R-mediated disease processes.

  11. Association of High-Mobility Group Box-1 With Th Cell-Related Cytokines in the Vitreous of Ocular Sarcoidosis Patients.

    Science.gov (United States)

    Takeuchi, Masaru; Taguchi, Manzo; Sato, Tomohito; Karasawa, Kyoko; Sakurai, Yutaka; Harimoto, Kohzou; Ito, Masataka

    2017-01-01

    High-mobility group box-1 (HMGB1) is a nonhistone DNA-binding nuclear protein released from necrotic cells, which is also secreted by activated leukocytes and acts as a primary proinflammatory cytokine. In this study, we compared vitreous HMGB1 levels in ocular sarcoidosis with those in noninflammatory vitreoretinal diseases and evaluated its association with Th cell-related and proinflammatory cytokines. The study group consisted of 24 patients with ocular sarcoidosis. The control group consisted of 27 patients with proliferative diabetic retinopathy (PDR) and 24 with idiopathic epiretinal membrane (ERM). Vitreous fluid samples were obtained at the beginning of vitrectomy. Vitreous levels of HMGB1 and IL-1β, IL-4, IL-6, IL-10, IL-17A, IL-17F, IL-21, IL-22, IL-23, IL-25, IL-31, IL-33, IFN-γ, soluble CD40 ligand (sCD40L), and TNFα were measured. High-mobility group box-1 was detected in the vitreous of 23 of 24 patients (95.8%) with ocular sarcoidosis. Mean vitreous level of HMGB1 was the highest in the sarcoidosis group, followed by the PDR and ERM groups, with significant differences between the three groups. In the sarcoidosis group, vitreous levels of IL-6, IL-10, IL-31, IFN-γ, sCD40L, and TNFα were significantly higher than those in the idiopathic ERM group, and IFN-γ and sCD40L were significantly higher than those in the PDR group. Vitreous HMGB-1 level correlated significantly with IL-10, IFN-γ, and sCD40L levels but not with IL-6, IL-17, IL-31, or TNFα levels. The vitreous level of HMGB1 is elevated in ocular sarcoidosis and is associated with vitreous levels of Th1- and regulatory T-related cytokines, but not with proinflammatory or Th17-related cytokines.

  12. Mesolysis of radical anions of tetra-, penta-, and hexaphenylethanes.

    Science.gov (United States)

    Tojo, Sachiko; Fujitsuka, Mamoru; Majima, Tetsuro

    2013-03-01

    A central carbon–carbon (C–C) σ bond dissociation of polyphenylethane radical anions (Ph(n)E•-, n = 3–6), mesolysis, was investigated by the transient absorption measurement during pulse radiolysis of Ph(n)E in 2-methyltetrahydrofuran. The charge resonance (CR) band of 1,1,2,2-tetraphenylethane radical anion (1,1,2,2-Ph4E•-) was observed in the near-infrared region immediately after an electron pulse to be attributed to the intramolecular dimer radical anion. The CR band disappeared with simultaneous formation of two absorption bands at 330 and 460 nm corresponding to diphenylmethyl radical and diphenylmethyl anion, respectively, indicating the occurrence of the mesolysis in 1,1,2,2-Ph4E•-. During pulse radiolysis of 1,1,1,2,2,2-hexaphenylethane (Ph6E), an absorption band of triphenylmethyl radical was observed at 340 nm immediately after an electron pulse. It is suggested that one electron attachment to Ph6E is followed by the subsequent rapid C–C σ bond dissociation. Formation of intramolecular dimer radical anions in Ph(n)E•- such as 1,1,2-triphenylethane (Ph3E), 1,1,1,2-tetraphenylethane (1,1,1,2-Ph4E), and 1,1,1,2,2-pentaphenylethane (Ph5E) was also studied together with the subsequent mesolysis. The mesolysis of Ph(n)E•- is discussed in terms of charge delocalization in the intramolecular dimer radical anions and the central C–C σ bond as well as bond dissociation energy of the central C–C σ bond of Ph(n)E•-.

  13. Anionic solid lipid nanoparticles supported on protamine/DNA complexes

    Energy Technology Data Exchange (ETDEWEB)

    Ye Jiesheng; Liu Chunxi; Chen Zhijin; Zhang Na [School of Pharmaceutical Science, Shandong University, 44 Wenhua Xi Road, Ji' nan (China); Wang Aihua [Department of Respiratory Medicine, Affiliated Qilu Hospital, Shandong University, 44 Wenhua Xi Road, Ji' nan (China)], E-mail: zhangnancy9@sdu.edu.cn

    2008-07-16

    The objective of this study was to design novel anionic ternary nanoparticles for gene delivery. These ternary nanoparticles were equipped with protamine/DNA binary complexes (150-200 nm) as the support, and the anionic formation was achieved by absorption of anionic solid lipid nanoparticles ({<=}20 nm) onto the surface of the binary complexes. The small solid lipid nanoparticles (SLNs) were prepared by a modified film dispersion-ultrasonication method, and adsorption of the anionic SLNs onto the binary complexes was typically carried out in water via electrostatic interaction. The formulated ternary nanoparticles were found to be relatively uniform in size (257.7 {+-} 10.6 nm) with a 'bumpy' surface, and the surface charge inversion from 19.28 {+-} 1.14 mV to -17.16 {+-} 1.92 mV could be considered as evidence of the formation of the ternary nanoparticles. The fluorescence intensity measurements from three batches of the ternary nanoparticles gave a mean adsorption efficiency of 96.75 {+-} 1.13%. Circular dichroism spectra analysis showed that the protamine/DNA complexes had been coated by small SLNs, and that the anionic ternary nanoparticles formed did not disturb the construction of the binary complexes. SYBR Green I analysis suggested that the ternary nanoparticles could protect the DNA from nuclease degradation, and cell viability assay results showed that they exhibit lower cytotoxicity to A549 cells compared with the binary complexes and lipofectamine. The transfection efficiency of the ternary nanoparticles was better than that of naked DNA and the binary complexes, and almost equal to that of lipofectamine/DNA complexes, as revealed by inversion fluorescence microscope observation. These results indicated that the anionic ternary nanoparticles could facilitate gene transfer in cultured cells, and might alleviate the drawbacks of the conventional cationic vector/DNA complexes for gene delivery in vivo.

  14. Carbon Dioxide Capture with Ionic Liquids and Deep Eutectic Solvents: A New Generation of Sorbents.

    Science.gov (United States)

    Sarmad, Shokat; Mikkola, Jyri-Pekka; Ji, Xiaoyan

    2017-01-20

    High cost and high energy penalty for CO 2 uptake from flue gases are important obstacles in large-scale industrial applications, and developing efficient technology for CO 2 capture from technical and economic points is crucial. Ionic liquids (ILs) show the potential for CO 2 separation owing to their inherent advantages, and have been proposed as alternatives to overcome the drawbacks of conventional sorbents. Chemical modification of ILs to improve their performance in CO 2 absorption has received more attention. Deep eutectic solvents (DESs) as a new generation of ILs are considered as more economical alternatives to cope with the deficiencies of high cost and high viscosity of conventional ILs. This Review discusses the potential of functionalized ILs and DESs as CO 2 sorbents. Incorporation of CO 2 -philic functional groups, such as amine, in cation and/or anion moiety of ILs can promot their absorption capacity. In general, the functionalization of the anion part of ILs is more effective than the cation part. DESs represent favorable solvent properties and are capable of capturing CO 2 , but the research work is scarce and undeveloped compared to the studies conducted on ILs. It is possible to develop novel DESs with promising absorption capacity. However, more investigation needs to be carried out on the mechanism of CO 2 sorption of DESs to clarify how these novel sorbents can be adjusted and fine-tuned to be best tailored as optimized media for CO 2 capture. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Time-dependent Anion Chemistry in the CSE IRC+10216

    Science.gov (United States)

    Guelin, M.; Agundez, M.; Cernicharo, J.; Gottlieb, C.; McCarthy, M.; Thaddeus, P.

    2011-05-01

    Following the spectral characterization of C-chain anions, in the Harvard microwave laboratory, we have discovered 6 anions in the envelope of the C-rich star IRC+10216 and set limits to the abundance of two others. The anions we studied in this source range from CCH- to C8H- and from CN- to C5N- [1,2,3]. Anion abundances are low and the rotational lines weak, even in favorable cases. Two years ago, we have been able to map C6H- in IRC+10216, with the PdB interferometer, and to show that it is located, like the C6H radical, in a hollow shell. The angular resolution of the observations (5) and the S/N ratio were however insufficient to spatially differentiate the anion from the radical. Taking advantage of the recent installation of a wide-band correlator on PdBI, we have re-observed with a twice higher resolution the 83 GHz line of C6H- , as well as nearby lines of C5N-, C4H-, C2H- and of several C-chain molecules and radicals. Except for CCH-, all those species are detected and we are currently analyzing their distributions and abundances. Chemistry models, based on the electron radiative attachment theory developed by Herbst and collaborators, predict that anions and parent radicals peak at different radii in the expanding CSE[4]. Predicted radial shifts range from a few arcsec, for C6H-, to more than 10 (500 yr) for C4H- and CN-. We know, from previous single-dish observations, that the actual abundances of C4H- and CN- , relative to C4H and CN, differ by orders of magnitude from radiative attachment model predictions, while those of the long anions, C6H- and C8H agree well with predictions. The new interferometric observations, allied to single-dish data, allow us to measure the formation/destruction time of the different species and to set constraints on the rates of electron radiative attachment, rates which, so far, are only crudely evaluated through the statistical theory. The relatively high abundances of CN-, C3N - and C5N - , compared to CCH-, C4H - and

  16. Photocatalytic degradation of anionic surfactant using zinc oxide nanoparticles

    Science.gov (United States)

    Giahi, M.; Habibi, S.; Toutounchi, S.; Khavei, M.

    2012-04-01

    In this paper the photocatalytic degradation of anionic surfactant LABS was studied by a batch process using ZnO nanoparticles with diameter size of 20 nm catalyst on irradiation with UV light and their behavior comparatively examined with respect to ZnO commercial powder. The effect of parameters such as initial surfactant concentration, initial solution pH has been studied. Also degradation at LABS in the presence of an electron acceptor like potassium peroxydisulfate and effect of anion presence on surfactant degradation has been systematically investigated. The obtained result demonstrated a high photocatalytic activity of nanosize semiconducting particles.

  17. Anion Conduction in Solid Electrolytes Probed by Water Transport Measurement

    OpenAIRE

    Takahashi, Hiroki; Takeguchi, Tatsuya; Yamanaka, Toshiro; Ueda, Wataru

    2010-01-01

    The application of inorganic materials as electrolyte of alkaline fuel cell is an important task to achieve noble-metal-free and high-temperature-resistant fuel cells. In the present study, water transport during ion conduction through solid electrolyte was measured to seek inorganic materials with anion conduction. We discovered the anion conduction in layered oxide NaCo2O4. Although LiCoO2 has the similar layered structure to NaCo2O4, this oxide showed cation conduction.

  18. 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.

  19. Controlling Actinide Hydration in Mixed Solvent Systems: Towards Tunable Solvent Systems to Close the Fuel Cycle

    Energy Technology Data Exchange (ETDEWEB)

    Clark, Sue B. [Washington State Univ., Pullman, WA (United States). Dept. of Chemistry

    2016-10-31

    The goal of this project has been to define the extent of hydration the f-elements and other cations in mixed solvent electrolyte systems. Methanol-water and other mixed solvent systems have been studied, where the solvent dielectric constant was varied systematically. Thermodynamic and spectroscopic studies provide details concerning the energetics of complexation and other reactions of these cations. This information has also been used to advance new understanding of the behavior of these cations in a variety of systems, ranging from environmental studies, chromatographic approaches, and ionization processes for mass spectrometry.

  20. Tetrabutylammonium Salts of Aluminum(III) and Gallium(III) Phthalocyanine Radical Anions Bonded with Fluoren-9-olato(-) Anions and Indium(III) Phthalocyanine Bromide Radical Anions.

    OpenAIRE

    Konarev, Dmitri V; Khasanov, Salavat S; Ishikawa, Manabu; Nakano, Yoshiaki; Otsuka, Akihiro; Yamochi, Hideki; Saito, Gunzi; Lyubovskaya, Rimma N

    2017-01-01

    Reduction of aluminum(III), gallium(III), and indium(III) phthalocyanine chlorides by sodium fluorenone ketyl in the presence of tetrabutylammonium cations yielded crystalline salts of the type (Bu4 N(+) )2 [M(III) (HFl-O(-) )(Pc(.3-) )](.-) (Br(-) )⋅1.5 C6 H4 Cl2 [M=Al (1), Ga (2); HFl-O(-) =fluoren-9-olato(-) anion; Pc=phthalocyanine] and (Bu4 N(+) ) [In(III) Br(Pc(.3-) )](.-) ⋅0.875 C6 H4 Cl2 ⋅0.125 C6 H14 (3). The salts were found to contain Pc(.3-) radical anions with negatively charged ...