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Sample records for rhin polyanion eurhin

  1. Radon hazard map in Bas-Rhin, final report

    International Nuclear Information System (INIS)

    2010-01-01

    After a presentation of radon (geochemical properties, origin, emanation and transfer to surface, related health hazard, exposure factor, modalities for the struggle against radon), of the study context, framework and objective, and of the Bas-Rhin geological context, this report presents the exploited data: definition of the geological uranium potential, direct measurements and geochemical analysis, indicators (lithologic characterization, surface radioactivity, drifting alluvial deposits), factors promoting inhalation, measurements in buildings. It presents and comments maps of the radon geological potential and of radon hazard. It proposes an assessment of radon potential hazard for different areas of the district, and reports measurements performed in Strasbourg, Eckbolsheim, Bischeim and Haguenau

  2. Design Tools for Reconfigurable Hardware in Orbit (RHinO)

    Science.gov (United States)

    French, Mathew; Graham, Paul; Wirthlin, Michael; Larchev, Gregory; Bellows, Peter; Schott, Brian

    2004-01-01

    The Reconfigurable Hardware in Orbit (RHinO) project is focused on creating a set of design tools that facilitate and automate design techniques for reconfigurable computing in space, using SRAM-based field-programmable-gate-array (FPGA) technology. These tools leverage an established FPGA design environment and focus primarily on space effects mitigation and power optimization. The project is creating software to automatically test and evaluate the single-event-upsets (SEUs) sensitivities of an FPGA design and insert mitigation techniques. Extensions into the tool suite will also allow evolvable algorithm techniques to reconfigure around single-event-latchup (SEL) events. In the power domain, tools are being created for dynamic power visualiization and optimization. Thus, this technology seeks to enable the use of Reconfigurable Hardware in Orbit, via an integrated design tool-suite aiming to reduce risk, cost, and design time of multimission reconfigurable space processors using SRAM-based FPGAs.

  3. RhinAsthma patient perspective: A Rasch validation study.

    Science.gov (United States)

    Molinengo, Giorgia; Baiardini, Ilaria; Braido, Fulvio; Loera, Barbara

    2018-02-01

    In daily practice, Health-Related Quality of Life (HRQoL) tools are useful for supplementing clinical data with the patient's perspective. To encourage their use by clinicians, the availability of tools that can quickly provide valid results is crucial. A new HRQoL tool has been proposed for patients with asthma and rhinitis: the RhinAsthma Patient Perspective-RAPP. The aim of this study was to evaluate the psychometric robustness of the RAPP using the Item Response Theory (IRT) approach, to evaluate the scalability of items and test whether or not patients use the items response scale correctly. 155 patients (53.5% women, mean age 39.1, range 16-76) were recruited during a multicenter study. RAPP metric properties were investigated using IRT models. Differential item functioning (DIF) was used for gender, age, and asthma control test (ACT). The RAPP adequately fitted the Rating Scale model, demonstrating the equality of the rating scale structure for all items. All statistics on items were satisfactory. The RAPP had adequate internal reliability and showed good ability to discriminate among different groups of participants. DIF analysis indicated that there were no differential item functioning issues for gender. One item showed a DIF by age and four items by ACT. The psychometric evaluation performed using IRT models demonstrated that the RAPP met all the criteria to be considered a reliable and valid method of measurement. From a clinical perspective, this will allow physicians to confidently interpret scores as good indicators of Quality of Life of patients with asthma.

  4. Cross-border dissemination of methicillin-resistant Staphylococcus aureus, Euregio Meuse-Rhin region

    NARCIS (Netherlands)

    Deurenberg, Ruud H; Nulens, Eric; Valvatne, Havard; Sebastian, Silvie; Driessen, Christel; Craeghs, Jos; De Brauwer, Els; Heising, Bernhard; Kraat, Yvette J; Riebe, Joachim; Stals, Frans S; Trienekens, Thera A; Scheres, Jacques; Friedrich, Alexander W; van Tiel, Frank H; Beisser, Patrick S; Stobberingh, Ellen E

    Because the prevalence of methicillin-resistant Staphylococcus aureus (MRSA) differs among the 3 countries forming the Euregio Meuse-Rhin (EMR) region (Belgium, Germany, and the Netherlands), cross-border healthcare requires information about the spread of MRSA in the EMR. We investigated the

  5. DB-PABP: a database of polyanion-binding proteins.

    Science.gov (United States)

    Fang, Jianwen; Dong, Yinghua; Salamat-Miller, Nazila; Middaugh, C Russell

    2008-01-01

    The interactions between polyanions (PAs) and polyanion-binding proteins (PABPs) have been found to play significant roles in many essential biological processes including intracellular organization, transport and protein folding. Furthermore, many neurodegenerative disease-related proteins are PABPs. Thus, a better understanding of PA/PABP interactions may not only enhance our understandings of biological systems but also provide new clues to these deadly diseases. The literature in this field is widely scattered, suggesting the need for a comprehensive and searchable database of PABPs. The DB-PABP is a comprehensive, manually curated and searchable database of experimentally characterized PABPs. It is freely available and can be accessed online at http://pabp.bcf.ku.edu/DB_PABP/. The DB-PABP was implemented as a MySQL relational database. An interactive web interface was created using Java Server Pages (JSP). The search page of the database is organized into a main search form and a section for utilities. The main search form enables custom searches via four menus: protein names, polyanion names, the source species of the proteins and the methods used to discover the interactions. Available utilities include a commonality matrix, a function of listing PABPs by the number of interacting polyanions and a string search for author surnames. The DB-PABP is maintained at the University of Kansas. We encourage users to provide feedback and submit new data and references.

  6. Polyanion-Type Electrode Materials for Sodium-Ion Batteries.

    Science.gov (United States)

    Ni, Qiao; Bai, Ying; Wu, Feng; Wu, Chuan

    2017-03-01

    Sodium-ion batteries, representative members of the post-lithium-battery club, are very attractive and promising for large-scale energy storage applications. The increasing technological improvements in sodium-ion batteries (Na-ion batteries) are being driven by the demand for Na-based electrode materials that are resource-abundant, cost-effective, and long lasting. Polyanion-type compounds are among the most promising electrode materials for Na-ion batteries due to their stability, safety, and suitable operating voltages. The most representative polyanion-type electrode materials are Na 3 V 2 (PO 4 ) 3 and NaTi 2 (PO 4 ) 3 for Na-based cathode and anode materials, respectively. Both show superior electrochemical properties and attractive prospects in terms of their development and application in Na-ion batteries. Carbonophosphate Na 3 MnCO 3 PO 4 and amorphous FePO 4 have also recently emerged and are contributing to further developing the research scope of polyanion-type Na-ion batteries. However, the typical low conductivity and relatively low capacity performance of such materials still restrict their development. This paper presents a brief review of the research progress of polyanion-type electrode materials for Na-ion batteries, summarizing recent accomplishments, highlighting emerging strategies, and discussing the remaining challenges of such systems.

  7. Electrochemical properties of copper-based compounds with polyanion frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Mizuno, Yoshifumi; Hata, Shoma; Suzuki, Kota; Hirayama, Masaaki; Kanno, Ryoji, E-mail: kanno@echem.titech.ac.jp

    2016-03-15

    The copper-based polyanion compounds Li{sub 6}CuB{sub 4}O{sub 10} and Li{sub 2}CuP{sub 2}O{sub 7} were synthesized using a conventional solid-state reaction, and their electrochemical properties were determined. Li{sub 6}CuB{sub 4}O{sub 10} showed reversible capacity of 340 mA g{sup −1} at the first discharge–charge process, while Li{sub 2}CuP{sub 2}O{sub 7} showed large irreversible capacity and thus low charge capacity. Ex situ X-ray diffraction (XRD) and X-ray absorption near edge structure (XANES) measurements revealed that the electrochemical Li{sup +} intercalation/deintercalation reaction in Li{sub 6}CuB{sub 4}O{sub 10} occurred via reversible Cu{sup 2+}/Cu{sup +} reduction/oxidation reaction. These differences in their discharge/charge mechanisms are discussed based on the strength of the Cu–O covalency via their inductive effects. - Graphical abstract: Electrochemical properties for Cu-based polyanion compounds were investigated. The electrochemical reaction mechanisms are strongly affected by their Cu–O covalentcy. - Highlights: • Electrochemical properties of Cu-based polyanion compounds were investigated. • The Li{sup +} intercalation/deintercalation reaction progressed in Li{sub 6}CuB{sub 4}O{sub 10}. • The electrochemical displacement reaction progressed in Li{sub 2}CuP{sub 2}O{sub 7}. • The strength of Cu–O covalency affects the reaction mechanism.

  8. Photophysics of aggregated 9-methylthiacarbocyanine bound to polyanions

    Science.gov (United States)

    Chibisov, Alexander K.; Görner, Helmut

    2002-05-01

    The photophysical properties of 3,3 '-diethyl-9-methylthiacarbocyanine (DTC) were studied in the presence of polystyrene sulfonate (PSS), polyacrylic acid (PAA) and polymethacrylic acid (PMA). The absorption spectra reflect a monomer/dimer equilibrium in neat aqueous solution and a shift towards bound H-aggregates, bound dimers and bound monomers on increasing the ratio of polyanion residue to dye concentrations ( r). These equilibria also determine the photodeactivation modes of DTC. The fluorescence intensity is reduced, when dimers and aggregates are present and strongly enhanced for low dye loading ( r=10 4). In contrast, the quantum yield of intersystem crossing is enhanced for bound dimers ( r=10 3).

  9. Estimation des caractéristiques biologiques des truites de mer adultes (Salmo trutta du Rhin supérieur

    Directory of Open Access Journals (Sweden)

    OMBREDANE D.

    1998-07-01

    Full Text Available L'analyse des longueurs totales et des écailles d'un échantillon de 120 truites de mer adultes capturées essentiellement par pêche à l'électricité dans le Rhin supérieur (700 km de la mer du Nord de 1989 à 1996 a permis de caractériser la population de cette ressource piscicole en voie de restauration. L'utilisation des Captures Par Unité d'Effort (CPUE, calculées pour les pêches de 1994 à 1996, permet d'appréhender le rythme de migration et d'améliorer l'estimation des caractéristiques générales de la population. Dans cette partie du Rhin, la migration anadrome de la truite de mer se déroule en deux pics successifs de juin à décembre, les individus les plus âgés arrivant les premiers. La population est caractérisée par une très forte prédominance des groupes d'âge de mer 1 + (49,2 % et 2+ (45,8 %, soit un Age Moyen de Mer (AMM de 1,54 an. L'Age Moyen de Smoltification (AMS et de première Reproduction (AMR sont estimés respectivement à 1,30 an et 1,39 an. Par ailleurs, il est constaté que l'âge marin de première maturité des adultes du Rhin augmente quand leur âge de smoltification diminue. Les résultats sont discutés en fonction de la méthodologie employée et comparés à ceux obtenus sur d'autres populations françaises et plus nordiques. Il ressort que les caractéristiques de la population de truite de mer du Rhin traduisent bien la position latitudinale mais aussi l'importance de ce réseau hydrographique.

  10. Chitosan/polyanion surface modification of styrene-butadiene-styrene block copolymer membrane for wound dressing.

    Science.gov (United States)

    Yang, Jen Ming; Yang, Jhe-Hao; Huang, Huei Tsz

    2014-01-01

    The surface of styrene-butadiene-styrene block copolymer (SBS) membrane is modified with tri-steps in this study. At first, two step modified SBS membrane (MSBS) was prepared with epoxidation and ring opening reaction with maleated ionomer. Then chitosan was used as the polycation electrolyte and sodium alginate, poly(γ-glutamic acid) (PGA) and poly(aspartic acid) (PAsp) were selected as polyanion electrolytes to deposit on the surfaces of MSBS membrane by the layer-by-layer self-assembly (LbL) deposition technique to get three [chitosan/polyanion] LbL modified SBS membranes, ([CS/Alg], [CS/PGA] and [CS/PAsp]). From the quantitative XPS analysis and water contact angle measurement, it is found that the order of wettability and the content of functional group percentages of COO(-) and OCN on the three [CS/polyanion] systems are [CS/Alg]>[CS/PGA]>[CS/PAsp]. Performances of water vapor transmission rates, fibronectin adsorption, antibacterial assessment and 3T3 fibroblast cell growth on [CS/Alg], [CS/PGA] and [CS/PAsp] membranes were also evaluated. With the evaluation of water vapor transmission rate, these [CS/Alg], [CS/PGA] and [CS/PAsp] membranes are sterile semipermeable with water evaporation at about 82±8g/day·m(2). It is found that the amount of fibronectin adsorption on the three [CS/polyanion] systems is significantly determined by the sum of the functional group of COO(-) and OCN on the surfaces of [CS/Alg], [CS/PGA] and [CS/PAsp] systems. The results are inverse with the sum of the functional group of COO(-) and OCN on the three [CS/polyanion]. From the cytotoxicity test and cell adhesion and proliferation assay of 3T3 fibroblasts on the three [CS/polyanion] systems, it revealed that the cells not only remained viable but they also proliferated on the surfaces of [CS/Alg], [CS/PGA] and [CS/PAsp]. The bactericidal activity was found on [CS/Alg], [CS/PGA] and [CS/PAsp]. The transport of bacterial through these [CS/polyanion] membranes was also conducted

  11. Chitosan/polyanion surface modification of styrene–butadiene–styrene block copolymer membrane for wound dressing

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Jen Ming, E-mail: jmyang@mail.cgu.edu.tw [Department of Chemical and Materials Engineering, Chang Gung University, Kwei-Shan, Tao-Yuan 333, Taiwan (China); Yang, Jhe-Hao [Department of Electronic Engineering, Chang Gung University, Kwei-Shan, Tao-Yuan 333, Taiwan (China); Huang, Huei Tsz [Department of Chemical and Materials Engineering, Chang Gung University, Kwei-Shan, Tao-Yuan 333, Taiwan (China)

    2014-01-01

    The surface of styrene–butadiene–styrene block copolymer (SBS) membrane is modified with tri-steps in this study. At first, two step modified SBS membrane (MSBS) was prepared with epoxidation and ring opening reaction with maleated ionomer. Then chitosan was used as the polycation electrolyte and sodium alginate, poly(γ-glutamic acid) (PGA) and poly(aspartic acid) (PAsp) were selected as polyanion electrolytes to deposit on the surfaces of MSBS membrane by the layer-by-layer self-assembly (LbL) deposition technique to get three [chitosan/polyanion] LbL modified SBS membranes, ([CS/Alg], [CS/PGA] and [CS/PAsp]). From the quantitative XPS analysis and water contact angle measurement, it is found that the order of wettability and the content of functional group percentages of COO{sup −} and -O=C-N- on the three [CS/polyanion] systems are [CS/Alg] > [CS/PGA] > [CS/PAsp]. Performances of water vapor transmission rates, fibronectin adsorption, antibacterial assessment and 3T3 fibroblast cell growth on [CS/Alg], [CS/PGA] and [CS/PAsp] membranes were also evaluated. With the evaluation of water vapor transmission rate, these [CS/Alg], [CS/PGA] and [CS/PAsp] membranes are sterile semipermeable with water evaporation at about 82 ± 8 g/day · m{sup 2}. It is found that the amount of fibronectin adsorption on the three [CS/polyanion] systems is significantly determined by the sum of the functional group of COO{sup −} and -O=C-N- on the surfaces of [CS/Alg], [CS/PGA] and [CS/PAsp] systems. The results are inverse with the sum of the functional group of COO{sup −} and -O=C-N- on the three [CS/polyanion]. From the cytotoxicity test and cell adhesion and proliferation assay of 3T3 fibroblasts on the three [CS/polyanion] systems, it revealed that the cells not only remained viable but they also proliferated on the surfaces of [CS/Alg], [CS/PGA] and [CS/PAsp]. The bactericidal activity was found on [CS/Alg], [CS/PGA] and [CS/PAsp]. The transport of bacterial through

  12. Effect of buffer at nanoscale molecular recognition interfaces - electrostatic binding of biological polyanions.

    Science.gov (United States)

    Rodrigo, Ana C; Laurini, Erik; Vieira, Vânia M P; Pricl, Sabrina; Smith, David K

    2017-10-19

    We investigate the impact of an over-looked component on molecular recognition in water-buffer. The binding of a cationic dye to biological polyanion heparin is shown by isothermal calorimetry to depend on buffer (Tris-HCl > HEPES > PBS). The heparin binding of self-assembled multivalent (SAMul) cationic micelles is even more buffer dependent. Multivalent electrostatic molecular recognition is buffer dependent as a result of competitive interactions between the cationic binding interface and anions present in the buffer.

  13. Spectrophotometric determination of various polyanions with polymeric film optodes using microtiter plate reader.

    Science.gov (United States)

    Dürüst, Nedime; Meyerhoff, Mark E; Unal, Nazangül; Naç, Sibel

    2011-08-05

    Polycation-sensitive membrane optodes based on the chromoionophore 2',7'-dichlorofluorescein octadecylester (DCFOE) have previously been developed and used for determination of heparin via a titrimetric method. In this study, it is shown that some other important polyanions such as PPS (pentosan polysulfate), DNA, xanthan, Na-alginate, and carrageenan (food additive) can also be readily determined by using DCFOE-based microtiter plate-format optodes (MPOs) and polycationic titrants that bind these polyanionic species. The optical sensors are prepared with poly(vinyl chloride) (PVC), polyurethane (PU), bis(2-ethylhexyl)sebacate (DOS), and 2',7'-dichlorofluorescein octadecylester (DCFOE) and exhibit reproducible and sensitive absorbance changes in response to the varying polycationic titrant concentrations. Three different polycations; protamine, poly-l-lysine and poly-l-arginine, are employed as titrants. The method has a detection limit of 1 μg mL(-1), and a dynamic range of 1-40 μg mL(-1). After the quantitative determinations are successfully demonstrated in buffered solutions, similar titrations are also performed in real samples. The method is validated by recovery studies in these samples. The average polyanion recoveries were quantitative [99.7(±1.3) % for pastry cream with vanillin (protamine titrant); 100.4 (±3.3) % for pastry gel with strawberry(PLA titrant), and 102.9(±2.0) % for pastry gel with strawberry (PLL titrant)]. Copyright © 2011 Elsevier B.V. All rights reserved.

  14. New polyanion-based cathode materials for alkali-ion batteries

    Science.gov (United States)

    Yaghoobnejad Asl, Hooman

    A number of new materials have been discovered through exploratory synthesis with the aim to be studied as the positive electrode (cathode) in Li-ion and Na-ion batteries. The focus has been set on the ease of synthesis, cost and availability of active ingredients in the battery, and decent cycle-life performance through a combination of iron and several polyanionic ligands. An emphasis has been placed also on phosphite (HPO32-) as a polyanionic ligand, mainly due to the fact that it has not been studied seriously before as a polyanion for cathode materials. The concept of mixed polyanions, for example, boro-phosphate and phosphate-nitrates were also explored. In each case the material was first made and purified via different synthetic strategies, and the crystal structure, which dominantly controls the performance of the materials, has been extensively studied through Single-Crystal X-ray Diffraction (SCXRD) or synchrotron-based Powder X-ray Diffraction (PXRD). This investigation yielded four new compositions, namely Li3Fe 2(HPO3)3Cl, LiFe(HPO3)2, Li0.8Fe(H2O)2B[P2O8]•H 2O and AFePO4NO3 (A = NH4/Li, K). Furthermore, for each material the electrochemical performance for insertion of Li+ ion has been studied by means of various electrochemical techniques to reveal the nature of alkali ion insertion. In addition Na-ion intercalation has been studied for boro-phosphate and AFePO4NO3. Additionally a novel synthesis procedure has been reported for tavorite LiFePO4F 1-x(OH)x, where 0 ≤ x ≤ 1, an important class of cathode materials. The results obtained clearly demonstrate the importance of crystal structure on the cathode performance through structural and compositional effects. Moreover these findings may contribute to the energy storage community by providing insight into the solid-state science of electrode material synthesis and proposing new alternative compositions based on sustainable materials.

  15. Monte Carlo simulations of flexible polyanions complexing with whey proteins at their isoelectric point.

    Science.gov (United States)

    de Vries, R

    2004-02-15

    Electrostatic complexation of flexible polyanions with the whey proteins alpha-lactalbumin and beta-lactoglobulin is studied using Monte Carlo simulations. The proteins are considered at their respective isoelectric points. Discrete charges on the model polyelectrolytes and proteins interact through Debye-Huckel potentials. Protein excluded volume is taken into account through a coarse-grained model of the protein shape. Consistent with experimental results, it is found that alpha-lactalbumin complexes much more strongly than beta-lactoglobulin. For alpha-lactalbumin, strong complexation is due to localized binding to a single large positive "charge patch," whereas for beta-lactoglobulin, weak complexation is due to diffuse binding to multiple smaller charge patches. Copyright 2004 American Institute of Physics

  16. Polyion complex micelles prepared by self-assembly of block-graft polycation and hyperbranched polyanion

    Science.gov (United States)

    Dai, Yu; Wang, Hongquan; Zhang, Xiaojin

    2017-09-01

    Polyion complex (PIC) micelles were prepared by self-assembly of block-graft polycation monomethoxy poly(ethylene glycol)- block-(poly(ɛ-caprolactone)- graft-polyethylenimine) (PEG- b-(PCL- g-PEI)) and hyperbranched polyanion sodium carboxyl-modified hyperbranched polyesters (Hx-COONa, x = 20, 30, 40). The results from commonly used MTT assay indicated that PIC micelles had good biocompatibility. PIC micelles with N/COO- of 8/3 had appropriate size (sub-110 nm) and moderate zeta potential ( 3 mV). PIC micelles were nano-sized spheres, and the average size was about 50 nm. PIC micelles had high drug loading capacity for hydrophilic drugs such as doxorubicin (DOX) hydrochloride and released the drugs under the influence of pH and ionic strength.

  17. Gazettes sous influence : le Courrier du Bas-Rhin, la Gazette des Deux-Ponts et les sujets touchant la Russie vers 1770

    Directory of Open Access Journals (Sweden)

    Georges Dulac

    2016-11-01

    Full Text Available Vers 1770, la campagne anti-russe du gouvernement français tend à dégrader l’image de la Russie, ce qui lèse gravement ses intérêts, notamment quand elle doit emprunter pour financer la guerre avec la Turquie. Aussi le prince Dmitri Alexeevitch Golitsyn, ministre plénipotentiaire à La Haye, se montre-t-il alors très actif sur ce terrain. Sa correspondance avec Pétersbourg témoigne de ses efforts, aux effets inégaux, pour influer sur les informations diffusées par quelques journaux : principalement le Courrier du Bas-Rhin, publié par Jean Manzon à Trèves, sous contrôle prussien, et dans une moindre mesure les deux Gazettes des Deux-Ponts, l’une politique, l’autre littéraire. Le journaliste de Trèves, qui trouve son intérêt à prendre le parti de la Russie, met en œuvre en sa faveur un discours journalistique abondant et parfois très élaboré. Cependant, la ligne du journal subit des fluctuations sensibles, selon l’évolution de la situation et à la suite de diverses interventions, dont celles du roi de Prusse et d’autre part de Stanislas-Auguste, qui pensionne un temps le journaliste. La Gazette des deux Ponts pratique l’information orientée avec plus de finesse, et, comme la gazette littéraire, accorde une large place à la matière russe : mais sur le plan politique, son traitement reste le plus souvent sous influence française et répond rarement aux vœux de D. A. Golitsyn.

  18. Synthesis and characterization of prospective polyanionic electrode materials for high performance energy storage applications

    Science.gov (United States)

    Jayachandran, M.; Durai, G.; Vijayakumar, T.

    2018-04-01

    In the present study, Polyanionic compound (SO4)-group based on Li2Ni(SO4)2 (Lithium Nickel Sulphate) composite electrodes materials were prepared by a ball-milling method and solid-state reaction route. X-ray diffraction analysis confirmed the formation of a polycrystalline orthorhombic phase of composite Li2Ni(SO4)2 with an average crystallite size of about 50.16 nm. Field Emission Scanning electron microscopy investigation reveals the spherical shape particles with the particle size of around 200–500 nm. Raman and FTIR analysis confirms the structural and functional groups of the synthesized materials and also the formation of Li2Ni(SO4)2. The electrochemical measurements using cyclic voltammetry (CV) and galvanostatic charging-discharging (GCD) techniques were carried out to study the electrochemical supercapacitive performance of the composite Li2Ni (SO4)2 electrodes. From the CV investigations, an areal capacitance of 508 mF cm‑2 was obtained at 10 mV s‑1. The galvanostatic charge-discharge (GCD) measurements exhibited the areal capacitance of 101 mF cm‑2 at a constant current density of 2 mA cm‑2 in 2 M KOH. These GCD profiles were linear and also symmetric in nature with the maximum columbic efficiency of about 85%. The electrochemical performance of the composite Li2Ni(SO4)2 electrode material shows excellent performance for supercapacitor applications.

  19. Unconventional Magnetism and Band Gap Formation in LiFePO4: Consequence of Polyanion Induced Non-planarity.

    Science.gov (United States)

    Jena, Ajit; Nanda, B R K

    2016-01-21

    Oxygen plays a critical role in strongly correlated transition metal oxides as crystal field effect is one of the key factors that determine the degree of localization of the valence d/f states. Based on the localization, a set of conventional mechanisms such as Mott-Hubbard, Charge-transfer and Slater were formulated to explain the antiferromagnetic and insulating (AFI) phenomena in many of these correlated systems. From the case study on LiFePO4, through density-functional calculations, we demonstrate that none of these mechanisms are strictly applicable to explain the AFI behavior when the transition metal oxides have polyanions such as (PO4)(3-). The symmetry-lowering of the metal-oxygen complex, to stabilize the polyanion, creates an asymmetric crystal field for d/f states. In LiFePO4 this field creates completely non-degenerate Fe-d states which, with negligible p-d and d-d covalent interactions, become atomically localized to ensure a gap at the Fermi level. Due to large exchange splitting, high spin state is favored and an antiferromagnetic configuration is stabilized. For the prototype LiFePO4, independent electron approximation is good enough to obtain the AFI ground state. Inclusion of additional correlation measures like Hubbard U simply amplifies the gap and therefore LiFePO4 can be preferably called as weakly coupled Mott insulator.

  20. La nécropole mérovingienne d’Erstein (Bas-Rhin) : étude des textiles minéralisés au contact des fibules

    OpenAIRE

    Médard, Fabienne; Rohmer, Pascal; Moulherat, Christophe; Guillaume, Jacques

    2008-01-01

    Au cours des années 1999 et 2000, des fouilles de sauvetage ont été menées au lieu dit « Beim Limersheimerweg », non loin de la ville d’Erstein (France, Bas-Rhin). Une importante nécropole datée entre le début du VIe et la fin du VIIe siècle après J.-C. a été mise au jour. 239 sépultures au mobilier funéraire très riche ont été découvertes. Alors que les matières organiques d’origine végétale et animale ont été peu préservées, les nombreuses pièces d’armement (épées longues, scramasaxes, cout...

  1. Computational study of HIV gp120 as a target for polyanionic entry inhibitors: Exploiting the V3 loop region.

    Directory of Open Access Journals (Sweden)

    Louis R Hollingsworth

    Full Text Available Multiple approaches are being utilized to develop therapeutics to treat HIV infection. One approach is designed to inhibit entry of HIV into host cells, with a target being the viral envelope glycoprotein, gp120. Polyanionic compounds have been shown to be effective in inhibiting HIV entry, with a mechanism involving electrostatic interactions with the V3 loop of gp120 being proposed. In this study, we applied computational methods to elucidate molecular interactions between the repeat unit of the precisely alternating polyanion, Poly(4,4'-stilbenedicarboxylate-alt-maleic acid (DCSti-alt-MA and the V3 loop of gp120 from strains of HIV against which these polyanions were previously tested (IIIb, BaL, 92UG037, JR-CSF as well as two strains for which gp120 crystal structures are available (YU2, 2B4C. Homology modeling was used to create models of the gp120 proteins. Using monomers of the gp120 protein, we applied extensive molecular dynamics simulations to obtain dominant morphologies that represent a variety of open-closed states of the V3 loop to examine the interaction of 112 ligands of the repeating units of DCSti-alt-MA docked to the V3 loop and surrounding residues. Using the distance between the V1/V2 and V3 loops of gp120 as a metric, we revealed through MD simulations that gp120 from the lab-adapted strains (BaL and IIIb, which are more susceptible to inhibition by DCSti-alt-MA, clearly transitioned to the closed state in one replicate of each simulation set, whereas none of the replicates from the Tier II strains (92UG037 and JR-CSF did so. Docking repeat unit microspecies to the gp120 protein before and after MD simulation enabled identification of residues that were key for binding. Notably, only a few residues were found to be important for docking both before and after MD simulation as a result of the conformational heterogeneity provided by the simulations. Consideration of the residues that were consistently involved in interactions

  2. Polyanionic pH-responsive polystyrene-b-poly(4-vinyl pyridine-N-oxide) isoporous membranes

    KAUST Repository

    Shevate, Rahul

    2015-12-01

    Recently isoporous block copolymer (BCP) membranes obtained by non-solvent induced phase separation gained a lot of attention due to their highly ordered surface layer, high flux and superior separation properties. These polystyrene-b-poly-4-vinylpyridine (PS-b-P4VP) based membranes showed a strong flux dependence of pH; pores closed at low pH and opened at high pH. The pH-response could now be reversed by a simple post modification; pores are now opening at low pH and closing at high pH. The original membrane was transformed into a polyanionic pH responsive membrane in a one step chemical modification without affecting the isoporous surface morphology. A polystyrene-b-poly-4-vinylpyridine-N-oxide (PS-b-P4VPN-oxide) membrane is obtained by selective oxidation of the PS-b-P4VP membrane. The in situ generated peracid obtained by reacting acetic acid and hydrogen peroxide is employed for oxidation. Surprisingly not only the asymmetric membrane structure with the isoporous skin was retained, but also the mechanical and chemical membrane stability was improved significantly. The modified membranes are insoluble in solvents like DMF, NMP and DMSO. Two kinds of PS-b-P4VP based isoporous membranes are available now with reverse flux response to pH. This opens the door to new interesting charge based fractionations.

  3. The effect of gradient boracic polyanion-doping on structure, morphology, and cycling performance of Ni-rich LiNi0.8Co0.15Al0.05O2 cathode material

    Science.gov (United States)

    Chen, Tao; Li, Xiang; Wang, Hao; Yan, Xinxiu; Wang, Lei; Deng, Bangwei; Ge, Wujie; Qu, Meizhen

    2018-01-01

    A gradient boracic polyanion-doping method is applied to Ni-rich LiNi0.8Co0.15Al0.05O2 (NCA) cathode material in this study to suppress the capacity/potential fade during charge-discharge cycling. Scanning electron microscope (SEM) results show that all samples present spherical morphology and the secondary particle size increases with increasing boron content. X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) results demonstrate that boracic polyanions are successfully introduced into the bulk material and more enriched in the outer layer. XPS analysis further reveals that the valence state of Ni3+ is partly reduced to Ni2+ at the surface due to the incorporation of boracic polyanions. From the electrochemical measurements, B0.015-NCA electrode exhibits excellent cycling performance, even at high potential and elevated temperature. Moreover, the SEM images illustrate the presence of cracks and a thick SEI layer on pristine particles after 100 cycles at high temperature, while the B0.015-NCA particles show an intact structure and thin SEI layer. Electrochemical impedance spectroscopy confirms that the boracic polyanion doping could hinder the impedance increase during cycling at elevated temperature. These results clearly indicate that the gradient boracic polyanion-doping contributes to the remarkable enhancement of structure stability and cycling performance of NCA.

  4. The influence of polyanion molecular weight on polyelectrolyte multilayers at surfaces: elasticity and susceptibility to saloplasticity of strongly dissociated synthetic polymers at fluid-fluid interfaces.

    Science.gov (United States)

    Cramer, Ashley D; Dong, Wen-Fei; Benbow, Natalie L; Webber, Jessie L; Krasowska, Marta; Beattie, David A; Ferri, James K

    2017-09-13

    We studied the interfacial mechanical properties of polyelectrolyte multilayer assemblies of poly(diallylamine hydrochloride) (PAH) and poly(4-styrenesulfonate)sodium salt (PSS) at the air-water interface using axisymmetric drop shape analysis (ADSA) during hydrostatic inflation as a function of aqueous salt concentration and two different polyanion molecular weights (M w ∼ 13 and 70 kDa). Surface elastic moduli (G s ) ranged from 50 to 300 mN m -1 . Using the measured film thickness, the bulk moduli (G) ranged from 10 to 90 MPa consistent with elastomeric solids. This solid-like interface was evidenced by a systematic departure of the inflated shape from the Young-Laplace equation, which assumes a liquid-like interface. Surface elastic moduli increased and bulk elastic moduli decreased with increasing nanomembrane transverse dimension, and multilayers with the lower molecular weight anion were more transversely compact than those of higher molecular weight and displayed a larger elastic modulus. The bulk moduli of both types of multilayer assemblies asymptotically approach a constant value for films with more than two bilayers of polyelectrolyte, consistent with the observed transition from a 'glassy' to 'rubbery' state. Both types of multilayer assemblies displayed plasticization with increasing sodium chloride concentration in the adjoining aqueous phase, i.e. saloplasticity, and exhibited a transition from elastic to plastic response to deformation. The restored mobility of the polyelectrolyte resulting from the shift from intrinsic to extrinsic charge complexation, restores fluidity to the interface and is evidenced by experimental observation of a liquid-like interface when loaded. The higher molecular weight polyanion multilayers plasticized at lower salt concentrations suggesting that the lower melting point of the higher molecular weight polyanion assembly is attributable to a lesser extent of electrostatic cross-linking underscoring the unconventional

  5. Enantiomeric and Diastereomeric Self-Assembled Multivalent (SAMul) Nanostructures - Understanding the Effects of Chirality on Binding to Polyanionic Heparin and DNA.

    Science.gov (United States)

    Thornalley, Kiri; Laurini, Erik; Pricl, Sabrina; Smith, David K

    2018-05-15

    A family of four self-assembling lipopeptides containing Ala-Lys peptides attached to a C16 aliphatic chain was synthesised. These compounds form two enantiomeric pairs that bear a diastereomeric relationship to one another (C16-L-Ala-L-Lys/C16-D-Ala-D-Lys) and (C16-D-Ala-L-Lys/C16-L-Ala-D-Lys). These diastereomeric pairs have very different critical micelle concentrations (CMCs), with LL/DD < DL/LD suggesting more effective assembly of the former. The self-assembled multivalent (SAMul) systems bind biological polyanions as result of the cationic lysine groups on their surfaces. Polyanion binding was investigated using dye displacement assays and isothermal calorimetry (ITC). On heparin binding, there was no significant enantioselectivity, but there was a binding preference for the diastereomeric assemblies with lower CMCs. Conversely, on binding DNA, there was a significant enantioselective preference for systems displaying D-lysine ligands, with a further slight preference for attachment to L-alanine, with the CMC being irrelevant. Binding to adaptive, ill-defined heparin has a large favourable entropic term, suggesting it depends primarily on the cationic SAMul nanostructure maximising surface contact with heparin, which can adapt, displacing solvent and other ions. Conversely, binding to well-defined, shape-persistent DNA has a larger favourable enthalpic term, and combined with the enantioselectivity, this allows us to suggest that its SAMul binding is based on optimised individual electrostatic interactions at the molecular level, with a preference for binding to D-lysine. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. 6-Peroxo-6-zirconium crown and its hafnium analogue embedded in a triangular polyanion: [M6(O2)6(OH)6(gamma-SiW10O36)3]18- (M = Zr, Hf).

    Science.gov (United States)

    Bassil, Bassem S; Mal, Sib Sankar; Dickman, Michael H; Kortz, Ulrich; Oelrich, Holger; Walder, Lorenz

    2008-05-28

    We have synthesized and structurally characterized the unprecedented peroxo-zirconium(IV) containing [Zr6(O2)6(OH)6(gamma-SiW10O36)3]18- (1). Polyanion 1 comprises a cyclic 6-peroxo-6-zirconium core stabilized by three decatungstosilicate units. We have also prepared the isostructural hafnium(IV) analogue [Hf6(O2)6(OH)6(gamma-SiW10O36)3]18- (2). We investigated the acid/base and redox properties of 1 by UV-vis spectroscopy and electrochemistry studies. Polyanion 1 represents the first structurally characterized Zr-peroxo POM with side-on, bridging peroxo units. The simple, one-pot synthesis of 1 and 2 involving dropwise addition of aqueous hydrogen peroxide could represent a general procedure for incorporating peroxo groups into a large variety of transition metal and lanthanide containing POMs.

  7. Synthesis, anion exchange, and delamination of Co-Al layered double hydroxide: assembly of the exfoliated nanosheet/polyanion composite films and magneto-optical studies.

    Science.gov (United States)

    Liu, Zhaoping; Ma, Renzhi; Osada, Minoru; Iyi, Nobuo; Ebina, Yasuo; Takada, Kazunori; Sasaki, Takayoshi

    2006-04-12

    This paper describes a systematic study on the synthesis, anion exchange, and delamination of Co-Al layered double hydroxide (LDH), with the aim of achieving fabrication and clarifying the properties of LDH nanosheet/polyanion composite films. Co-Al-CO3 LDH hexagonal platelets of 4 mum in lateral size were synthesized by the urea method under optimized reaction conditions. The as-prepared CO3(2-)-LDH was converted to Cl- -LDH by treating with a NaCl-HCl mixed solution, retaining its high crystallinity and hexagonal platelike morphology. LDHs intercalated with a variety of anions (such as NO3-, ClO4-, acetate, lactate, dodecyl sulfate, and oleate) were further prepared from Cl- -LDH via an anion-exchange process employing corresponding salts. Exchanged products in various anion forms were found to show different delamination behaviors in formamide. Among them, best results were observed for NO3- -LDH in terms of the exfoliating degree and the quality of the exfoliated nanosheets. The delamination gave a pink transparent suspension containing well-defined nanosheets with lateral sizes of up to 2 microm. The resulting nanosheets were assembled layer-by-layer with an anionic polymer, poly(sodium styrene 4-sulfonate) (PSS), onto quartz glass substrates to produce composite films. Magnetic circular dichroism (MCD) measurements revealed that the assembled multilayer films exhibited an interesting magneto-optical response.

  8. Fission of Polyanionic Metal Clusters

    Science.gov (United States)

    König, S.; Jankowski, A.; Marx, G.; Schweikhard, L.; Wolfram, M.

    2018-04-01

    Size-selected dianionic lead clusters Pbn2 -, n =34 - 56 , are stored in a Penning trap and studied with respect to their decay products upon photoexcitation. Contrary to the decay of other dianionic metal clusters, these lead clusters show a variety of decay channels. The mass spectra of the fragments are compared to the corresponding spectra of the monoanionic precursors. This comparison leads to the conclusion that, in the cluster size region below about n =48 , the fission reaction Pbn2 -→Pbn-10 -+Pb10- is the major decay process. Its disappearance at larger cluster sizes may be an indication of a nonmetal to metal transition. Recently, the pair of Pb10- and Pbn-10 - were observed as pronounced fragments in electron-attachment studies [S. König et al., Int. J. Mass Spectrom. 421, 129 (2017), 10.1016/j.ijms.2017.06.009]. The present findings suggest that this combination is the fingerprint of the decay of doubly charged lead clusters. With this assumption, the dianion clusters have been traced down to Pb212 -, whereas the smallest size for the direct observation was as high as n =28 .

  9. Multi-center vs. two-center bonding within the hetero-polyanion in Eu{sub 2}GaPt{sub 2} and its prototype Ca{sub 2}SiIr{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Poettgen, Rainer [Institut fuer Anorganische und Analytische Chemie, Universitaet Muenster (Germany); Borrmann, Horst; Grin, Yuri [Max-Planck-Institut fuer Chemische Physik fester Stoffe, Dresden (Germany)

    2017-11-17

    The compound Eu{sub 2}GaPt{sub 2} was synthesized from the elements in a sealed tantalum tube. Its Ca{sub 2}SiIr{sub 2}-type crystal structure was refined from single-crystal X-ray diffraction data: space group C2/c, a = 9.8775(6), b = 5.8621(6), c = 7.9677(5) Aa, β = 102.257(4) , R{sub F} = 0.039, 1344 observed reflections, and 25 variable parameters. The platinum (iridium) atoms in Eu{sub 2}GaPt{sub 2} and Ca{sub 2}SiIr{sub 2} form linear chains of dumbbells [2c(Pt-Pt) or 2c(Ir-Ir) bonds, respectively]. These chains are interconnected to 2D polyanions in Eu{sub 2}GaPt{sub 2} by the gallium atoms forming 4c(Ga-Pt-Ga-Pt) or by silicon atoms forming 2c(Si-Ir) bonds in Ca{sub 2}SiIr{sub 2}. The polyanion bonds to the europium (calcium) matrix via the pseudo lone-pairs at the gallium (silicon) atoms. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  10. (PO_4)"3"− polyanions doped LiNi_1_/_3Co_1_/_3Mn_1_/_3O_2: An ultrafast-rate, long-life and high-voltage cathode material for Li-ion rechargeable batteries

    International Nuclear Information System (INIS)

    Cong, Lina; Zhao, Qin; Wang, Zhao; Zhang, Yuhang; Wu, Xinglong; Zhang, Jingping; Wang, Rongshun; Xie, Haiming; Sun, Liqun

    2016-01-01

    Highlights: • LiNi_1_/_3Co_1_/_3Mn_1_/_3O_2 layered structure is doped with (PO_4)"3"− polyanions. • Results confirm that (PO_4)"3"− influences MO_6 octahedral environment in LiNi_1_/_3Co_1_/_3Mn_1_/_3O_2 lattice. • Charge–discharge properties are investigated under high voltage battery operation. • Cycling and rate performance of the doped materials is markedly enhanced. • Pre-cycling treatment inhibits microcracks at the grain boundaries at 4.7–2.8 V. - Abstract: Layered compounds LiNi_1_/_3Co_1_/_3Mn_1_/_3O_2 have recently received much attention as they have been regarded as a promising cathode materials for industrial application. However, its fast energy density decay and poor rate performance which originate from structure disruption especially at high rate and high cut-off voltage limit its large-scale application. Here, a novel designed concept and facile method were firstly used to fabricate (PO_4)"3"− polyanions doped layered LiNi_1_/_3Co_1_/_3Mn_1_/_3O_2 (LNMC-(PO_4) _0_._0_1_5-O_1_._9_4) structure, which could offer more stable high-voltage cycling performance and high rate capability. We attribute this improved performance to the robust P_t_e_t-O covalence, which will stabilize the oxygen close-packed structure during repeated cycling. Moreover, our stepwise pre-cycling treatments could effectively restrain the formation of micro-cracks and non-crystallization defects, and significantly improve cyclic durability with high charge voltage of 4.7V. The LNMC-(PO_4) _0_._0_1_5-O_1_._9_4 electrode can still delivers capacity retention of 81% after 200 cycles at a current density of 300mA g"−"1. The preliminary results reported here manifest that this novel-designed LNMC-(PO_4) _0_._0_1_5-O_1_._9_4 material represents an attractive alternative to ultrafast-rate, long-life and high-voltage electrode material for lithium ion batteries.

  11. The germanides Er{sub 5}Pd{sub 4}Ge{sub 8} and Tm{sub 5}Pd{sub 4}Ge{sub 8}. 3D [Pd{sub 4}Ge{sub 8}] polyanions with Ge{sub 2} dumb-bells and Ge{sub 4} chains in cis-conformation

    Energy Technology Data Exchange (ETDEWEB)

    Heying, Birgit; Rodewald, Ute C.; Poettgen, Rainer [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie

    2017-07-01

    Tm{sub 5}Pd{sub 4}Ge{sub 8} was synthesized by melting of the elements in an arc-melting furnace. The new germanide was characterized by powder and single-crystal X-ray diffraction: own structure type, P2{sub 1}/m, a=574.3(1), b=1380.4(3), c=836.4(1) pm, β=107.57(2) , V=0.6321 nm{sup 3}, wR2=0.0578, 2533 F{sup 2} values, 86 variables. The palladium and germanium atoms built up a three-dimensional [Pd{sub 4}Ge{sub 8}]{sup 15-} polyanionic network which contains a unique germanium substructure composed of the Zintl anions Ge{sub 2}{sup 6-} dumb-bells and Ge{sub 4}{sup 10-} chains in cis-conformation. The palladium atoms within the network have distorted square pyramidal germanium coordination. The three crystallographically independent thulium atoms have coordination numbers 15, 16 and 17 with partial motifs of the Frank-Kasper type polyhedra. The isotypic germanide Er{sub 5}Pd{sub 4}Ge{sub 8} forms only after annealing the arc-melted sample at 1070 K for 1 week: a=575.14(9), b=1386.3(3), c=838.4(1) pm, β=107.51(2) , V=0.6375 nm{sup 3}.

  12. Toward the synthesis of high boron content polyanionic multicluster macromolecules

    Czech Academy of Sciences Publication Activity Database

    Farras, P.; Cioran, A.M.; Šícha, Václav; Teixidor, F.; Štíbr, Bohumil; Grüner, Bohumír; Vinas, C.

    2009-01-01

    Roč. 48, č. 17 (2009), s. 8210-8219 ISSN 0020-1669 R&D Projects: GA MŠk LC523; GA AV ČR IAAX00320901 Grant - others:Generalitat de Catalunya(ES) 2005/SGR/00709; Spanish Ministerio de Ciencia y Tecnologia (ES) MAT2006-05339 Institutional research plan: CEZ:AV0Z40320502 Keywords : neutron-capture therapy * weakly coordinating anions * oxonium derivatives Subject RIV: CA - Inorganic Chemistry Impact factor: 4.657, year: 2009

  13. Newer polyanionic bio-composite anode for sodium ion batteries

    Science.gov (United States)

    Karuppiah, Saravanan; Vellingiri, Suganya; Nallathamby, Kalaiselvi

    2017-02-01

    NASICON frame work Na3V2(PO4)3 (NVP), wrapped by nitrogen and sulfur doped bio-carbon matrix derived from human hair (HHC) has been investigated for its anode behavior in SIBs. Basically, NVP is bestowed with a crystal structure of 3D open framework and a moderate theoretical capacity of 118 mAh g-1, which are the twin advantages and motivation behind the selection of this material. Prepared through a simple, scalable and facile method, the key problems associated with pristine NVP electrode material, such as inferior conductivity and severe volume change have been mitigated to a great extent through the formation of a composite containing HHC. Herein, HHC is a cheap and eco-friendly composite additive, obtained from a universal bio-waste, viz., human hair and hence NVP/HHC qualifies itself as a green composite. Interestingly, NVP/HHC-10 (in-situ) and NVP/HHC-20 (ex-situ) anodes show excellent electrochemical performance in terms of cycling stability up to 500 cycles and rate capability @ 2 A g-1, which are superior than similar category NVP anodes reported in the literature. Further, post cycling structure and morphology of NVP/HHC composite anodes evidence the appreciable stability bestowed with the select composition, which is found to get maintained upon extended cycles and even after rate capability test.

  14. The uranium bearing shale ore-body at St-Hippolyte (Haut-Rhin). An example of research with statistical methods; Le gisement des schistes uraniferes de St-Hippolyte (Haut-Rhin). Exemple d'etude par calculs statistiques

    Energy Technology Data Exchange (ETDEWEB)

    Carlier, A [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1958-07-01

    The uranium bearing shale ore-body at St-Hippolyte was mainly proved by drillings, the results of which were studied through statistical methods. The author gives an account of his conclusions regarding the distribution of mineralization, its origin and, the estimate of reserves. The uranium mineralization is irregularly distributed in shales. On a vertical line, levels could be singled out: they are similar, as far as lithology is concerned, but each of them is characterized by a grade-population, according to a lognormal distribution. Horizontally, a connection is noted between grades and the overlying barren sandstone bed. These considerations, as well as a statistical study of U/Ra ratio, induced the author to consider that the mineralization of the richest level has an hydrothermal origin. It is only through an uranium diffusion from that level that the others are mineralized. The uranium which is contained in poorest beds has a syn-genetic origin. Furthermore, statistical methods bring us to an evaluation of reserves. In such a case, the evaluation is equivalent to the ore obtained by common arithmetical methods. Moreover, we are able to state precisely the upper and lower limits where a true tonnage or a true grade could be given with a definite value of statistical certainty. Then the author has been able to study the separation of reserves in grade-groups and to foresee the effect of sorting in connection with the lower possible grade and with extraction units (wagons, lorries, etc...), on which the sorting will be done. To conclude, the author indicates the value of both classical and statistical methods. These two techniques are completing each other and they solve different problems. (author) [French] Le gisement des schistes uraniferes de St-Hippolyte a ete reconnu essentiellement par sondages, dont les resultats ont ete etudies par les methodes du calcul statistique. L'auteur expose les conclusions auxquelles il a ete amene et qui concernent: la repartition de la mineralisation, son origine et l'evaluation des reserves. La mineralisation est inegalement repartie dans les schistes. Dans le sens vertical, on distingue plusieurs niveaux, lithologiquement semblables, mais caracterises chacun par une population de teneurs qui obeit a la loi lognormale. Dans le sens horizontal, on note une relation entre les teneurs et la couverture greseuse sterile. Ces considerations, ainsi que l'etude statistique du rapport U/Ra, conduisent l'auteur a considerer que la mineralisation du niveau le plus riche est d'origine hydrothermale; les autres niveaux ne sont mineralises que par une diffusion de l'uranium, a partir du precedent. L'uranium contenu dans les couches les plus pauvres est d'origine syngenetique. Les calculs statistiques conduisent de plus a une estimation des reserves du gisement. Dans le cas considere, cette estimation est equivalente a celle que l'on obtient par la methode arithmetique classique. Mais on arrive en outre a preciser les limites superieures et inferieures entre lesquelles se situent, soit le tonnage vrai, soit la teneur vraie, a un niveau de certitude donne. Enfin, l'auteur a pu ainsi etudier la decomposition des reserves en tranches de teneurs, et prevoir l'effet du triage, en fonction de la teneur de coupure adoptee et des unites d'extraction (berlines, camions, etc) sur lesquelles sera opere le triage. L'auteur montre en conclusion, l'interet qui s'attache respectivement a la methode classique d'evaluation et a la methode statistique. Ces deux methodes se completent et repondent a des preoccupations differentes. (auteur)

  15. sociales del turismo industrial. Una comparación entre el Bages-Berguedà y el Haut-Rhin

    Directory of Open Access Journals (Sweden)

    José María Prat Forga

    2013-01-01

    Full Text Available En la actual sociedad neomoderna, donde la mayor parte de la población es urbana y dedicada al sector terciario, disponiendo de mayor poder de consumo y más tiempo libre para entretenimiento y ocio, en estos últimos años los turistas, con el deseo de atesorar vivencias únicas e individuales en los aspectos festivos, lúdicos, educativos y culturales, cada vez más, demandan unos productos personalizados. Ante esta situación, la oferta turística se está adaptando a estas nuevas necesidades, generando nuevos productos. Uno de ellos es el turismo industrial, cuyo consumo sirve para dar satisfacción a un colectivo con unas características diferenciales respecto a otros turistas más genéricos. Con su consumo, los turistas industriales satisfacen sus motivaciones culturales, realizando estancias cortas – principalmente en los fines de semana –, con especial énfasis en la calidad percibida en las visitas, en las tematizaciones y en las actividades compartidas.

  16. Release of polyanions from polyelectrolyte complexes by selective degradation of the polycation

    Czech Academy of Sciences Publication Activity Database

    Etrych, Tomáš; Boustta, M.; Leclercq, L.; Vert, M.

    2006-01-01

    Roč. 21, č. 2 (2006), s. 89-105 ISSN 0883-9115 Institutional research plan: CEZ:AV0Z40500505 Keywords : polyelectrolyte complex * enzymatic degradation * hydrolytic degradation Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.925, year: 2006

  17. Ca-C backbone fragmentation dominates in electron detachment dissociation of gas-phase polypeptide polyanions

    DEFF Research Database (Denmark)

    Kjeldsen, Frank; Silivra, Oleg A; Ivonin, Igor A

    2005-01-01

    the dissociation of oxidized radical anions [M-nH]((n-1)-*. We demonstrate that C(alpha)-C cleavages, which are otherwise rarely observed in tandem mass spectrometry, can account for most of the backbone fragmentation, with even-electron x fragments dominating over radical a* ions. Ab initio calculations at the B3...... LYP level of theory with the 6-311+G(2 p,2 d)//6-31+G(d,p) basis set suggested a unidirectional mechanism for EDD (cleavage always N-terminal to the radical site), with a*, x formation being favored over a, x* fragmentation by 74.2 kJ mol(-1). Thus, backbone C(alpha)-C bonds N-terminal to proline...

  18. Photodetachment of electron of polyanions: fundamental aspects and application to mass spectrometry

    International Nuclear Information System (INIS)

    Brunet, Claire

    2012-01-01

    This research thesis reports a study of optical properties and of photo-fragmentation of proteins in gas phase. After an overview of the different techniques of fragmentation and optical spectroscopy used for the characterisation of proteins, the author presents the experimental apparatus which implements a coupling of optical spectroscopy (UV/visible laser) and mass spectrometry (LTQ, linear trap quadrupole). Then, she reports the structural characterisation of proteins for a large range of wavelength (from UV to visible), and the study of the properties of the electron emitted by the measurement of its kinetic energy by photo-electron spectroscopy. She shows that the UV-visible radiation can also be used to study optical properties of radical anions by means of an experimental installation with two colours. The last part addresses the technique of dissociation by electron photodetachment which is notably compared with dissociation by electron detachment on a set of peptides of different sizes and negatively charged. The complementarity of these both techniques is discussed [fr

  19. Adsorption of Polyanion onto Large Alpha Alumina Beads with Variably Charged Surface

    Directory of Open Access Journals (Sweden)

    Tien Duc Pham

    2014-01-01

    Full Text Available Adsorption of strong polyelectrolyte, poly(styrenesulfonate, PSS, of different molecular weights onto large α-Al2O3 beads was systematically investigated as functions of pH and NaCl concentrations. The ultraviolet (UV absorption spectra of PSS at different pH and salt concentrations confirmed that the structure of PSS is independent of pH. With the change of molecular weight from 70 kg/mol (PSS 70 to 1000 kg/mol (PSS 1000, adsorption amount of PSS increases and proton coadsorption on the surface of α-Al2O3 decreases at given pH and salt concentration. It suggests that higher molecular weight of PSS was less flat conformation than lower one. The adsorption density of PSS 70 and PSS 1000 decreases with decreasing salt concentrations, indicating that both electrostatic and nonelectrostatic interactions are involved. Experimental results of both PSS 70 and PSS 1000 adsorption isotherms onto α-Al2O3 at different pH and salt concentrations can be represented well by two-step adsorption model. The effects of molecular weight and salt concentration are explained by structure of adsorbed PSS onto α-Al2O3. The influence of added SDS on the isotherms is evaluated from the sequential adsorption. The SDS uptake onto α-Al2O3 in the presence of hemimicelles can prevent the adsorption of PSS at low concentration so that adsorption of PSS reduces with preadsorbed SDS.

  20. Pearl-necklace complexes of flexible polyanions with neutral-cationic diblock copolymers

    NARCIS (Netherlands)

    Golinska, M.D.; Wolf, de F.A.; Cohen Stuart, M.A.; Hernandez Garcia, A.; Vries, de R.J.

    2013-01-01

    We study the complexation of very asymmetric diblock copolymers (consisting of a cationic block of 12 lysines connected to a 400 amino acid long hydrophilic polypeptide block with a net charge that is nearly zero) with oppositely charged sodium poly(acrylic acid) (NaPAA) with a range of molar masses

  1. Phase behavior and structure of stable complexes between a long polyanion and a branched polycation

    Science.gov (United States)

    Mengarelli, Valentina; Zeghal, Mehdi; Auvray, Loïc; Clemens, Daniel

    2011-08-01

    The association between oppositely charged branched polyethylenimine (BPEI) and polymethacrylic acid (PMA) in the dilute regime is investigated using turbidimetric titration and electrophoretic mobility measurements. The complexation is controlled by tuning continuously the pH-sensitive charge of the polyacid in acidic solution. The formation of soluble and stable positively charged complexes is a cooperative process characterized by the existence of two regimes of weak and strong complexation. In the regime of weak complexation, a long PMA chain overcharged by several BPEI molecules forms a binary complex. As the charge of the polyacid increases, these binary complexes condense at a well defined charge ratio of the mixture to form large positively charged aggregates. The overcharging and the existence of two regimes of complexation are analyzed in the light of recent theories. The structure of the polyelectrolytes is investigated at higher polymer concentration by small angle neutron scattering. Binary complexes of finite size present an open structure where the polyacid chains connecting a small number of BPEI molecules have shrunk slightly. In the condensed complexes, BPEI molecules, wrapped by polyacid chains, form networks of stretched necklaces.

  2. Efficacy of HIV antiviral polyanionic carbosilane dendrimer G2-S16 in the presence of semen

    Directory of Open Access Journals (Sweden)

    Ceña-Diez R

    2016-05-01

    Full Text Available Rafael Ceña-Diez,1–4,* Pilar García-Broncano,1–5,* Francisco Javier de la Mata,4,6 Rafael Gómez,4,6 Mª Ángeles Muñoz-Fernández1–4 1Hospital General Universitario Gregorio Marañon, 2Instituto de Investigación Sanitaria Gregorio Marañon, 3Spanish HIV HGM Biobank, 4Networking Research Center on Bioengineering, Biomaterials and Nanomedicine (CIBER-BBN, 5Laboratory of Viral Infection and Immunity, National Center of Microbiology, Health Institute of Carlos III, Majadahonda, 6Department of Organic Chemistry and Inorganic Chemistry, University of Alcalá, Alcalá de Henares, Madrid, Spain *These authors contributed equally to this work Abstract: The development of a safe and effective microbicide to prevent the sexual transmission of human immunodeficiency virus (HIV-1 is urgently needed. Unfortunately, the majority of microbicides, such as poly(L-lysine-dendrimers, anionic polymers, or antiretrovirals, have proved inactive or even increased the risk of HIV infection in clinical trials, most probably due to the fact that these compounds failed to prevent semen-exposed HIV infection. We showed that G2-S16 dendrimer exerts anti-HIV-1 activity at an early stage of viral replication, blocking the gp120/CD4/CCR5 interaction and providing a barrier to infection for long periods, confirming its multifactorial and nonspecific ability. Previously, we demonstrated that topical administration of G2-S16 prevents HIV transmission in humanized BLT mice without irritation or vaginal lesions. Here, we demonstrated that G2-S16 is active against mock- and semen-exposed HIV-1 and could be a promising microbicide against HIV infection. Keywords: G2-S16, dendrimer, HIV-1, SEVI, microbicide, antiretrovirals

  3. Concession renewal of Kembs' hydroelectric head on the Rhine river; Renouvellement de la concession de la chute hydro-electrique de Kembs sur le Rhin

    Energy Technology Data Exchange (ETDEWEB)

    Baron, P.; Defoug, H.; Petit, D

    2000-07-15

    In order to evaluate the different impacts of the concession renewal of Kembs' water head on the Rhine river, all aspects have been considered and are reported in this document: international aspects, influence of the dam on navigation and floods, hydrology of Alsace plain, ecological, energetic and economical aspects, leisure and safety aspects. Several questions have to be put forward which concern the transfrontier relations, the water rights, the problem of derivations, of Rhine river maintenance, the turbine and water depth warranty problems, the flow rate and the restoration of the Rhine island. All these questions must be tackled by the impact study. The implementation of a local procedure follow up made of a permanent technical working group and of a management committee is recommended. (J.S.)

  4. Del Rhin al Suárez o el viaje de Lengerke por los caminos de la Civilización y la “Barbarie”

    Directory of Open Access Journals (Sweden)

    Álvaro Neil Franco Zambrano

    2013-01-01

    Full Text Available El propósito del presente ensayo es abordar la novela “La otra raya del tigre” de Pedro Gómez Valderrama, desde una perspectiva que enfatiza la crisis de la modernidad y la literatura de viajes característica del siglo XIX. De tal manera, que conceptos como modernización económica, ciudad, liberalismo, colonización, feudalismo y civilización, junto con la visión del crítico moderno Néstor García Canclini y la percepción que Carmen Elisa Acosta tiene sobre los viajeros decimonónicos, son de vital importancia para comprender el itinerario del presente texto por la naturaleza exótica de Santander, por los caminos amarillos salidos de las entrañas de Van Gogh, por la fatalidad de las mujeres con alma de escorpión, por la hibridación de las culturas, especialmente la alemana y la santandereana, y por el lenguaje que destaca la tradición oral de los llamados pingos.

  5. : Management and prevention of the risk of flood : the example of the risk prevention plan of the valley of Largue river (haut - Rhin, France)

    OpenAIRE

    With , Lauriane

    2007-01-01

    accessible sur http://www.cresat.uha.fr/presentation/plonearticle.2008-12-08.7240336541/; La Largue constitue un cas d'école particulièrement intéressant en termes d'étude géohistorique des risques d'inondations. En ce qui concerne tout d'abord le choix du site par les pouvoirs publics, l'enquête historique montre que la Largue a connu de multiples crues, d'intensité et de fréquence variable, dont les plus célèbres sont celles de septembre 1852, février 1860, octobre 1880, juin 1973 (comprise...

  6. The natural seismic hazard and induced seismicity of the european HDR (hot dry rock) geothermal energy project at Soultz-sous-Forets (Bas-Rhin, France); Alea sismique naturel et sismicite induite du projet geothermique europeen RCS (roche chaude seche) de Soultz-sous-Forets (Bas-Rhin, France)

    Energy Technology Data Exchange (ETDEWEB)

    Helm, J A

    1996-06-07

    Development of the Soultz-sous-Forets HDR (Hot Dry Rock) geothermal energy project will involve important fluid injections which will induce micro-seismic events. This thesis discusses the natural seismicity of the region and induced seismicity associated with fluid injections. A catalogue of all historical and instrument seismicity of the Soultz-sous-Forets (SSF) region has been compiled. This seismicity does not correspond to movements along the major tectonic features of the region. The area around SSF has been identified as being one where high heat flow corresponds to low seismicity. The largest well documented seismic event in the region which took place in 1952 had an epicentral intensity of VI. All important data pertaining to the series of seismic events which took place in the region from August to October 1952 have been collected and are presented. This work details the installation and operation of a permanent 3 station network of accelerometers and seismometers around the HDR site. Also the installation and operation of a mobile network of vertical seismometers during fluid injections. 167 micro-seismic events were recorded on the surface network, with magnitudes from -0.5 to 1.9. The preferential alignment of the micro-seismic cloud is N160 deg. Individual focal mechanisms of the larger seismic events correspond to an extensional tectonic regime. Stress inversion of P wave polarities indicates that the maximum stress is vertical and the intermediate and minimum stress axes horizontal. The largest of the horizontal stresses is orientated N124 deg and the smallest N34 deg. Induced seismic movement is taking place on pre-existing fractures controlled by the in situ stress seismic movement is taking place on pre-existing tectonic fractures controlled by the in situ stress field, and the largest of the induced events had a magnitude 1.9. This level of seismicity does not pose any environmental hazard to the region around Soultz-sous-Forets. (author) 151 refs.

  7. Thermo-controlled rheology of electro-assembled polyanionic polysaccharide (alginate) and polycationic thermo-sensitive polymers.

    Science.gov (United States)

    Niang, Pape Momar; Huang, Zhiwei; Dulong, Virginie; Souguir, Zied; Le Cerf, Didier; Picton, Luc

    2016-03-30

    Several thermo-sensitive polyelectrolyte complexes were prepared by ionic self-association between an anionic polysaccharide (alginate) and a monocationic copolymer (polyether amine, Jeffamine®-M2005) with a 'Low Critical Solubility Temperature' (LCST). We show that electro-association must be established below the aggregation temperature of the free Jeffamine®, after which the organization of the system is controlled by the thermo-association of Jeffamine® that was previously electro-associated with the alginate. Evidence for this comes primarily from the rheology in the semi-dilute region. Electro- and thermo-associative behaviours are optimal at a pH corresponding to maximum ionization of both compounds (around pH 7). High ionic strength could prevent the electro-association. The reversibility of the transition is possible only at temperatures lower than the LCST of Jeffamine®. Similar behaviour has been obtained with carboxymethyl cellulose (CMC), which suggests that this behaviour can be observed using a range of anionic polyelectrolytes. In contrast, no specific properties have been found for pullulan, which is a neutral polysaccharide. Copyright © 2015 Elsevier Ltd. All rights reserved.

  8. 23Na+- and 39K+-NMR studies of cation-polyanion interactions in vascular connective tissue

    International Nuclear Information System (INIS)

    Siegel, G.; Walter, A.; Bostanjoglo, M.

    1987-01-01

    The ion binding properties of vascular connective tissue as well as of substances derived therefrom were studied in dependence on cation concentration by NMR and atomic absorption techniques. 16 refs.; 8 figs

  9. Polyanionic pH-responsive polystyrene-b-poly(4-vinyl pyridine-N-oxide) isoporous membranes

    KAUST Repository

    Shevate, Rahul; Karunakaran, Madhavan; Kumar, Mahendra; Peinemann, Klaus-Viktor

    2015-01-01

    , but also the mechanical and chemical membrane stability was improved significantly. The modified membranes are insoluble in solvents like DMF, NMP and DMSO. Two kinds of PS-b-P4VP based isoporous membranes are available now with reverse flux response to p

  10. Cobalt and Vanadium Trimetaphosphate Polyanions: Synthesis, Characterization, and Electrochemical Evaluation for Non-aqueous Redox-Flow Battery Applications.

    Science.gov (United States)

    Stauber, Julia M; Zhang, Shiyu; Gvozdik, Nataliya; Jiang, Yanfeng; Avena, Laura; Stevenson, Keith J; Cummins, Christopher C

    2018-01-17

    An electrochemical cell consisting of cobalt ([Co II/III (P 3 O 9 ) 2 ] 4-/3- ) and vanadium ([V III/II (P 3 O 9 ) 2 ] 3-/4- ) bistrimetaphosphate complexes as catholyte and anolyte species, respectively, was constructed with a cell voltage of 2.4 V and Coulombic efficiencies >90% for up to 100 total cycles. The [Co(P 3 O 9 ) 2 ] 4- (1) and [V(P 3 O 9 ) 2 ] 3- (2) complexes have favorable properties for flow-battery applications, including reversible redox chemistry, high stability toward electrochemical cycling, and high solubility in MeCN (1.09 ± 0.02 M, [PPN] 4 [1]·2MeCN; 0.77 ± 0.06 M, [PPN] 3 [2]·DME). The [PPN] 4 [1]·2MeCN and [PPN] 3 [2]·DME salts were isolated as crystalline solids in 82 and 68% yields, respectively, and characterized by 31 P NMR, UV/vis, ESI-MS(-), and IR spectroscopy. The [PPN] 4 [1]·2MeCN salt was also structurally characterized, crystallizing in the monoclinic P2 1 /c space group. Treatment of 1 with [(p-BrC 6 H 4 ) 3 N] + allowed for isolation of the one-electron-oxidized spin-crossover (SCO) complex, [Co(P 3 O 9 ) 2 ] 3- (3), which is the active catholyte species generated during cell charging. The success of the 1-2 cell provides a promising entry point to a potential future class of transition-metal metaphosphate-based all-inorganic non-aqueous redox-flow battery electrolytes.

  11. Manipulating cluster size of polyanion-stabilized Fe3O4 magnetic nanoparticle clusters via electrostatic-mediated assembly for tunable magnetophoresis behavior

    International Nuclear Information System (INIS)

    Yeap, Swee Pin; Ahmad, Abdul Latif; Ooi, Boon Seng; Lim, JitKang

    2015-01-01

    We report in this article an approach for manipulating the size of magnetic nanoparticle clusters (MNCs) via electrostatic-mediated assembly technique using an electrolyte as a clustering agent. The clusters were surface-tethered with poly(sodium 4-styrenesulfonate) (PSS) through electrostatic compensation to enhance their colloidal stability. Dynamic light scattering was employed to trace the evolution of cluster size. Simultaneously, electrophoretic mobility and Fourier transform infrared spectroscopy analyses were conducted to investigate the possible schemes involved in both cluster formation and PSS grafting. Results showed that the average hydrodynamic cluster size of the PSS/MNCs and their corresponding size distributions were successfully shifted by means of manipulating the suspension pH, the ionic nature of the electrolyte, and the electrolyte concentration. More specifically, the electrokinetic behavior of the particles upon interaction with the electrolyte plays a profound role in the formation of the PSS/MNCs. Nonetheless, the solubility of the polymer in electrolyte solution and the purification of the particles from residual ions should not be omitted in determining the effectiveness of this clustering approach. The PSS adlayer makes the resultant entities highly water-dispersible and provides electrosteric stabilization to shield the PSS/MNCs from aggregation. In this study, the experimental observations were analyzed and discussed on the basis of existing fundamental colloidal theories. The strategy of cluster size manipulation proposed here is simple and convenient to implement. Furthermore, manipulating the size of the MNCs also facilitates the tuning of magnetophoresis kinetics on exposure to low magnetic field gradient, which makes this nano-entity useful for engineering applications, specifically in separation processes.

  12. Conducting electrospun fibres with polyanionic grafts as highly selective, label-free, electrochemical biosensor with a low detection limit for non-Hodgkin lymphoma gene.

    Science.gov (United States)

    Kerr-Phillips, Thomas E; Aydemir, Nihan; Chan, Eddie Wai Chi; Barker, David; Malmström, Jenny; Plesse, Cedric; Travas-Sejdic, Jadranka

    2018-02-15

    A highly selective, label-free sensor for the non-Hodgkin lymphoma gene, with an aM detection limit, utilizing electrochemical impedance spectroscopy (EIS) is presented. The sensor consists of a conducting electrospun fibre mat, surface-grafted with poly(acrylic acid) (PAA) brushes and a conducting polymer sensing element with covalently attached oligonucleotide probes. The sensor was fabricated from electrospun NBR rubber, embedded with poly(3,4-ethylenedioxythiophene) (PEDOT), followed by grafting poly(acrylic acid) brushes and then electrochemically polymerizing a conducting polymer monomer with ssDNA probe sequence pre-attached. The resulting non-Hodgkin lymphoma gene sensor showed a detection limit of 1aM (1 × 10 -18 mol/L), more than 400 folds lower compared to a thin-film analogue. The sensor presented extraordinary selectivity, with only 1%, 2.7% and 4.6% of the signal recorded for the fully non-complimentary, T-A and G-C base mismatch oligonucleotide sequences, respectively. We suggest that such greatly enhanced selectivity is due to the presence of negatively charged carboxylic acid moieties from PAA grafts that electrostatically repel the non-complementary and mismatch DNA sequences, overcoming the non-specific binding. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Manipulating cluster size of polyanion-stabilized Fe{sub 3}O{sub 4} magnetic nanoparticle clusters via electrostatic-mediated assembly for tunable magnetophoresis behavior

    Energy Technology Data Exchange (ETDEWEB)

    Yeap, Swee Pin, E-mail: sweepin0727@hotmail.com; Ahmad, Abdul Latif; Ooi, Boon Seng; Lim, JitKang, E-mail: chjitkangl@usm.my [Universiti Sains Malaysia, School of Chemical Engineering (Malaysia)

    2015-10-15

    We report in this article an approach for manipulating the size of magnetic nanoparticle clusters (MNCs) via electrostatic-mediated assembly technique using an electrolyte as a clustering agent. The clusters were surface-tethered with poly(sodium 4-styrenesulfonate) (PSS) through electrostatic compensation to enhance their colloidal stability. Dynamic light scattering was employed to trace the evolution of cluster size. Simultaneously, electrophoretic mobility and Fourier transform infrared spectroscopy analyses were conducted to investigate the possible schemes involved in both cluster formation and PSS grafting. Results showed that the average hydrodynamic cluster size of the PSS/MNCs and their corresponding size distributions were successfully shifted by means of manipulating the suspension pH, the ionic nature of the electrolyte, and the electrolyte concentration. More specifically, the electrokinetic behavior of the particles upon interaction with the electrolyte plays a profound role in the formation of the PSS/MNCs. Nonetheless, the solubility of the polymer in electrolyte solution and the purification of the particles from residual ions should not be omitted in determining the effectiveness of this clustering approach. The PSS adlayer makes the resultant entities highly water-dispersible and provides electrosteric stabilization to shield the PSS/MNCs from aggregation. In this study, the experimental observations were analyzed and discussed on the basis of existing fundamental colloidal theories. The strategy of cluster size manipulation proposed here is simple and convenient to implement. Furthermore, manipulating the size of the MNCs also facilitates the tuning of magnetophoresis kinetics on exposure to low magnetic field gradient, which makes this nano-entity useful for engineering applications, specifically in separation processes.

  14. Polyelectrolyte complex formation and stability when mixing polyanions and polycations in salted media: A model study related to the case of body fluids

    Czech Academy of Sciences Publication Activity Database

    Etrych, Tomáš; Leclercq, L.; Boustta, M.; Vert, M.

    2005-01-01

    Roč. 25, 1-2 (2005), s. 281-288 ISSN 0928-0987 EU Projects: European Commission(XE) 512087 - GIANT Institutional research plan: CEZ:AV0Z40500505 Keywords : polyelectrolyte complex * selectivity * light scattering Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.347, year: 2005

  15. Molecular dynamics modeling the synthetic and biological polymers interactions pre-studied via docking: anchors modified polyanions interference with the HIV-1 fusion mediator.

    Science.gov (United States)

    Tsvetkov, Vladimir B; Serbin, Alexander V

    2014-06-01

    In previous works we reported the design, synthesis and in vitro evaluations of synthetic anionic polymers modified by alicyclic pendant groups (hydrophobic anchors), as a novel class of inhibitors of the human immunodeficiency virus type 1 (HIV-1) entry into human cells. Recently, these synthetic polymers interactions with key mediator of HIV-1 entry-fusion, the tri-helix core of the first heptad repeat regions [HR1]3 of viral envelope protein gp41, were pre-studied via docking in terms of newly formulated algorithm for stepwise approximation from fragments of polymeric backbone and side-group models toward real polymeric chains. In the present article the docking results were verified under molecular dynamics (MD) modeling. In contrast with limited capabilities of the docking, the MD allowed of using much more large models of the polymeric ligands, considering flexibility of both ligand and target simultaneously. Among the synthesized polymers the dinorbornen anchors containing alternating copolymers of maleic acid were selected as the most representative ligands (possessing the top anti-HIV activity in vitro in correlation with the highest binding energy in the docking). To verify the probability of binding of the polymers with the [HR1]3 in the sites defined via docking, various starting positions of polymer chains were tried. The MD simulations confirmed the main docking-predicted priority for binding sites, and possibilities for axial and belting modes of the ligands-target interactions. Some newly MD-discovered aspects of the ligand's backbone and anchor units dynamic cooperation in binding the viral target clarify mechanisms of the synthetic polymers anti-HIV activity and drug resistance prevention.

  16. Assembly of a new inorganic-organic frameworks based on [Sb4Mo12(OH)6O48]10- polyanion

    Science.gov (United States)

    Thabet, Safa; Ayed, Meriem; Ayed, Brahim; Haddad, Amor

    2014-10-01

    A new organic-inorganic hybrid material, (C4N2H7)8[K(H2O)]2[Sb4Mo12(OH)6O48]ṡ16H2O (1) has been isolated by the conventional solution method and characterized by elemental analysis, single-crystal X-ray diffraction, infrared spectroscopy, UV-visible spectroscopies, cyclic voltammetry and TG-DTA analysis. The compound crystallizes in the triclinic space group P - 1 with a = 13.407(6) Å, b = 13.906(2) Å, c = 14.657(7) Å, α = 77.216(9)°, β = 71.284(6)°, γ = 71.312(3)° and Z = 1. The crystal structure exhibits an infinite 1D inorganic structure built from [Sb4Mo12(OH)6O48]10- clusters and potassium cations; adjacent chains are further joined up hydrogen bonding interactions between protonated 2-methylimidazolim cations, water molecules and polyoxoanions to form a 3D supramolecular architecture.

  17. Formation and proof of stable bi-, tri- and tetraradical polyanions during the electrochemical reduction of cone-polynitrocalix[4]arenes. An ESR-UV-vis spectroelectrochemical study

    International Nuclear Information System (INIS)

    Liška, Alan; Rosenkranz, Marco; Klíma, Jiří; Dunsch, Lothar; Lhoták, Pavel; Ludvík, Jiří

    2014-01-01

    Graphical abstract: - Abstract: The first intermediates of electrochemical reduction of nitro compounds in nonaqueous DMF are stable radical anions. In the series of mono-, di-, tri- and tetranitro calix[4]arenes each nitro group represents a reduction center, therefore the question about the spin state of intermediary anions arises. In this communication, the voltammetric and coulometric investigation of these compounds is performed together with the spectral measurements (ESR and UV-vis). The in-situ spectroelectrochemical approach proved that during reduction, in all polynitro radicalic intermediates the electrons remain unpaired and thus relatively stable mono-, di-, tri- and tetraradical mono-, di-, tri- and tetraanions, respectively, can be electrochemically generated in aprotic DMF from polynitrocalix[4]arenes. This finding confirms that the nitrophenyl units in polynitrocalix[4]arenes are completely independent and no mutual electronic communication takes place among them

  18. Download this PDF file

    African Journals Online (AJOL)

    AJTCAM

    bUMR 7213 C.N.R.S. Laboratoire de Biophotonique et Pharmacologie, 74 route du Rhin, BP. 60024 ; 67401 ..... practically without danger by oral route. ... Etude de l'action antihypertensive des graines de Parkia ... American Industrial.

  19. Thermometric titration in investigation of the formation of polyanions of molybdenum(VI), tungsten(VI), vanadium(V), and chromium (VI)-I: comparison of thermometric and potentiometric titration curves.

    Science.gov (United States)

    Kiba, N; Takeuchi, T

    1973-09-01

    A new twin-cell thermometric titrator has been devised and used for thermometric titration of solutions of sodium molybdate, sodium tungstate, sodium orthovanadate, ammonium metavanadate, and potassium chromate with perchloric acid. The thermometric titration curves were compared with corresponding pH-titration curves for elucidation of the reactions occurring in the titrations. Thermometric titrimetric methods have been developed for the determination of tungsten, vanadium and chromium.

  20. On the irrationality measure for a q-analogue of ζ(2)

    International Nuclear Information System (INIS)

    Zudilin, W V

    2002-01-01

    A Liouville-type estimate is proved for the irrationality measure of quantities. The proof is based on the application of a q-analogue of the arithmetic method developed by Chudnovsky, Rukhadze, and Hata and of the transformation group for hypergeometric series-the group-structure approach introduced by Rhin and Viola

  1. Evolution of work utilization - multiple purpose works

    International Nuclear Information System (INIS)

    Meclot, B.; Masson, J.; Eon, J.

    1992-01-01

    EDF exploitation of hydraulic resource is mainly for electric purposes, but also for electricity, irrigation, tourism and sport activities (for example: DURANCE and VERDON), electricity and navigation (for example: RHIN), and for providing collectivity needs (new reserves creation, existing barrages improvement, present management adaptation

  2. Pressure influence on magnetic properties of Nd.sub.2./sub.RhIn.sub.8./sub.

    Czech Academy of Sciences Publication Activity Database

    Javorský, P.; Kaštil, Jiří; Míšek, Martin; Prachařová, M.; Prchal, J.; Klicpera, M.; Kratochvílová, M.

    2016-01-01

    Roč. 411, Aug (2016), s. 98-102 ISSN 0304-8853 Institutional support: RVO:68378271 Keywords : hydrostatic pressure * uniaxial pressure * specific heat * magnetization * R2RhIn8 Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.630, year: 2016

  3. A new inorganic-organic nanohybrid based on a copper(II) semicarbazone complex and the PMo.sub.12./sub.O.sup.3-./sup..sub.40./sub. polyanion: synthesis, characterization, crystal structure and photocatalytic activity for degradation of cationic dyes

    Czech Academy of Sciences Publication Activity Database

    Farhadi, S.; Mahmoudi, F.; Dušek, Michal; Eigner, Václav; Kučeráková, Monika

    2017-01-01

    Roč. 122, Jan (2017), s. 247-256 ISSN 0277-5387 R&D Projects: GA ČR(CZ) GA14-03276S; GA MŠk LO1603 EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : inorganic-organic hybrid * semicarbazone complex * nanohybrid * photodegradation * cationic dyes Subject RIV: CA - Inorganic Chemistry OBOR OECD: Inorganic and nuclear chemistry Impact factor: 1.926, year: 2016

  4. Novel manganate Cs{sub 23}Mn{sub 16}O{sub 28} containing two different types of quasi one-dimensional polyanions, {sup 1}{sub ∞}[MnO{sub 2}]{sub n} and unique {sup 1}{sub ∞}[Mn{sub 3}O{sub 5}]{sub n}

    Energy Technology Data Exchange (ETDEWEB)

    Nuss, Juergen; Jansen, Martin [Max-Planck-Institut fuer Festkoerperforschung, Stuttgart (Germany); Senaris-Rodriguez, Maria A. [Dept. Quimica, Facultad de Ciencias, Universidad de A Coruna (Spain); Klemenz, Sebastian [Max-Planck-Institut fuer Chemische Physik fester Stoffe, Dresden (Germany)

    2017-11-17

    Cs{sub 23}Mn{sub 16}O{sub 23} was synthesized via the azide/nitrate route from mixtures of Mn{sub 2}O{sub 3}, CsNO{sub 3}, and CsN{sub 3}. This manganese(II/III) mixed-valent oxide, which contains only one Mn{sup 3+} besides 15 Mn{sup 2+} cations, was studied by single-crystal X-ray diffraction and magnetic susceptibility measurements. Its crystal structure [P anti 1, Z = 1, a = 1114.26(2), b = 1185.53(2), c = 1205.39(2) pm, α = 70.596(1), β = 80.377(2), γ = 83.072(2) , R{sub 1} = 0.033] is based on a honeycomb-like arrangement of cesium atoms, providing the space for two different types of one-dimensional polyoxomanganate anions, illustrated by the syntax Cs{sub 23}[MnO{sub 2}]{sub 4}[Mn{sub 3}O{sub 5}]{sub 4}. Magnetic susceptibility measurements indicate dominant antiferromagnetic intra-chain interactions present already at ambient temperature and long range inter-chain magnetic ordering at 11 K. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  5. A novel organic–inorganic hybrid with Anderson type polyanions as building blocks: (C{sub 6}H{sub 10}N{sub 3}O{sub 2}){sub 2}Na(H{sub 2}O){sub 2}[Al(OH){sub 6}Mo{sub 6}O{sub 18}]·6H{sub 2}O

    Energy Technology Data Exchange (ETDEWEB)

    Thabet, Safa, E-mail: safathabet@hotmail.fr [Laboratoire de matériaux et cristallochimie, Département de chimie, Institut Supérieur des Sciences Appliquées et Technologier, Avenue El Mourouj, 5111 Mahdia (Tunisia); Ayed, Brahim, E-mail: brahimayed@yahoo.fr [Laboratoire de matériaux et cristallochimie, Département de chimie, Institut Supérieur des Sciences Appliquées et Technologier, Avenue El Mourouj, 5111 Mahdia (Tunisia); Haddad, Amor [Laboratoire de matériaux et cristallochimie, Département de chimie, Institut Supérieur des Sciences Appliquées et Technologier, Avenue El Mourouj, 5111 Mahdia (Tunisia)

    2012-11-15

    Graphical abstract: Display Omitted Highlights: ► Synthesis of a novel inorganic–organic hybrid compound based on Anderson polyoxomolybdates. ► Characterization by X-ray diffraction, IR and UV–Vis spectroscopies of the new compound. ► Potential applications in catalysis, biochemical analysis and electrical conductivity of the organic–inorganic compound. -- Abstract: A new organic–inorganic hybrid compound based on Anderson polyoxomolybdates, (C{sub 6}H{sub 10}N{sub 3}O{sub 2}){sub 2}Na(H{sub 2}O){sub 2}[Al(OH){sub 6}Mo{sub 6}O{sub 18}]·6H{sub 2}O (1) have been isolated by the conventional solution method and characterized by single-crystal X-ray diffraction, infrared, ultraviolet spectroscopy and Thermogravimetric Analysis (TGA). This compound crystallized in the triclinic system, space group P−1, with a = 94.635(1) Å, b = 10.958(1) Å, c = 11.602(1) Å, α = 67.525(1)°, β = 71.049(1)°, γ = 70.124(1)° and Z = 1. The crystal structures of the compounds exhibit three-dimensional supramolecular assembly based on the extensive hydrogen bonding interactions between organic cations, sodium cations, water molecules and Anderson polyoxoanions. The infrared spectrum fully confirms the X-ray crystal structure and the UV spectrum of the title compound exhibits an absorption peak at 210 nm.

  6. CRREL (Cold Regions Research and Engineering Laboratory) Technical Publications. Supplement, October 1986-September 1988

    Science.gov (United States)

    1988-09-01

    surveys, [: reporting Soil chemistry , Vaste disposal, Utter pollution, The ice mas in this atlas were prepared to Jocumeat Detection, Solubility the 1333...Peimmite 3’. p.53-59 1 absea peLtnfrost, pemafrost tietmalll propeties, Sea Refs. p.64-67. mt’:, dater temperature, Watetr chemistry , Salinity. 41-die...recrystillization Bitiminans concretes, Low temperature tests, Concrete in b)t3 atarally and laboratory deformed ice. rhin strength, Thermal stresses, Cracking

  7. Effect of relative humidity on migration of BP from paperboard into a food simulant

    DEFF Research Database (Denmark)

    Barnkob, Line Lundbæk; Petersen, Jens Højslev

    In the scientific literature it is obligatory to control and report the test time and temperature applied when testing migration but it is not current practice to either control or report the relative humidity (RH).......In the scientific literature it is obligatory to control and report the test time and temperature applied when testing migration but it is not current practice to either control or report the relative humidity (RH)....

  8. Algological studies on the site of the Fessenheim nuclear power station

    International Nuclear Information System (INIS)

    Pierre, J.F.

    1980-01-01

    Systematic study of the algal flora at five stations situated on both sides of the nuclear power station at Fessenheim (department of Haut-Rhin, France). The analysis of the diatomaceae populations in 1977 and 1978, i.e. before and after the start of the reactors, does not indicate, in the composition and abundance of algae, any modifications susceptible to be directly connected to the implantation of the nuclear power station [fr

  9. Molecular tracing of classical swine fever viruses isolated from wild boars and pigs in France from 2002 to 2011.

    Science.gov (United States)

    Simon, Gaëlle; Le Dimna, Mireille; Le Potier, Marie-Frédérique; Pol, Françoise

    2013-10-25

    There were three outbreaks of classical swine fever (CSF) in north-eastern France between 2002 and 2011. The first two occurred in April 2002 in the Moselle department, in a wild boar and pig herd, respectively, while the third occurred in April 2003, in the Bas-Rhin department, in a wild boar. A survey was subsequently implemented in wild boar and domestic pig populations, during which 43 CSF viruses (CSFVs) were genetically characterized to provide information on virus sources, trace virus evolution and help in the monitoring of effective control measures. Phylogenetic analyses, based on fragments of the 5'NTR, E2 and NS5B genes, showed that all French CSFVs could be assigned to genotype 2, subgenotype 2.3. CSFVs isolated in Moselle were classified in the "Rostock" lineage, a strain first described in 2001 in wild boar populations in the Eifel region of north-western Rhineland-Palatinate in Germany, and in Luxemburg. In contrast, the CSFVs isolated in Bas-Rhin were homologous to strains from the "Uelzen" lineage, a strain previously isolated from wild boars in south-eastern Rhineland-Palatinate, Germany, as well as in Vosges du Nord, France, during a previous outbreak that had occurred in wild boars between 1992 and 2001. The outbreak in Moselle domestic pigs was quickly resolved as it concerned only one herd. The infection in wild boars from Moselle was extinguished after a few months whereas wild boars from Bas-Rhin remained infected until 2007. Molecular tracing showed that the Bas-Rhin index virus strain evolved slightly during the period but that no strain from a novel lineage was introduced until this outbreak ended after application of a vaccination scheme for six years. Copyright © 2013 Elsevier B.V. All rights reserved.

  10. 75 FR 61700 - Purified Carboxymethylcellulose From Finland, the Netherlands, and Sweden: Final Results of the...

    Science.gov (United States)

    2010-10-06

    ... also referred to as purified sodium CMC, polyanionic cellulose, or cellulose gum, which is a white to....gov/frn . The paper copy and electronic version of the Decision Memo are identical in content. Final...

  11. The use of a scanning proton microprobe in AIDS research

    Science.gov (United States)

    Cholewa, M.; Legge, G. J. F.; Weigold, H.; Holan, G.; Birch, C.

    1993-05-01

    A series of organometallic and inorganic drugs has been synthesized at the CSIRO Division of Chemicals and Polymers. The drugs, which are all polyanions of various size, shape and charge are being tested for their activity for the HIV virus in a continuous human T-lymphocyte line (MT2) and in peripheral blood lymphocytes (PBLs). Determinations of drug activity have been carried out at the Fairfield Hospital's Virology Department. It is important for the drug synthesis programme to develop an understanding of the relationship between polyanion properties and antiviral activity. For this it is essential to establish: (a) whether polyanions enter HIV infected cells, (b) their distribution within these cells, (c) whether this distribution is the same for all polyanions, (d) whether the drugs remain intact (do not dissociate) on entering the cell, (e) the differences between active and inactive drugs of similar structure. Answers to these questions and to others will facilitate the synthesis programme.

  12. Effect of adsorption of charged macromolecules on streaming and membrane potential values measured with a microporous polysulfone membrane

    DEFF Research Database (Denmark)

    Benavente, J.; Jonsson, Gunnar Eigil

    1997-01-01

    with a polyanion (dextran sulfate or DS) and a polycation (diethylaminoethyl or DEAE-dextran). From electrokinetic and electrochemical measurements, information about characteristic membrane parameters (transport number and ionic permselectivity) and membrane/solution interactions (zeta potential) can be obtained...

  13. Physics in the fast lane: rotors, fast ions and mobile fermions

    International Nuclear Information System (INIS)

    Price, D.L.; Saboungi, M.-L.

    1996-09-01

    Dynamic disorder in the high-temperature solid phases of the Zintl compounds CsPb and NaSn is characterized by. fast orientational motions of the polyanions and coupled motions of the cations Melting is characterized by slow translational motions of the centers of mass of the polyanions. The dynamic behavior of the ions is associated with dramatic increases in electrical conductivity characteristic of the behavior expected of a mixed conductor

  14. Synthesis and Characterization of the Ternary Thiobismuthates A9Bi13S24 (A = K, Rb)

    KAUST Repository

    Davaasuren, Bambar; Alahmary, Fatimah S.; Dashjav, Enkhtsetseg; Khanderi, Jayaprakash; Rothenberger, Alexander

    2016-01-01

    .9072(9) Å, β = 105.826(3)° for KBiS (1) and a = 31.823(6) Å, b = 4.1177(8) Å, c = 21.086(4) Å, β = 105.62(3)° for RbBiS (2). The crystal structure of 1 contains a 3D [KBiS] polyanionic framework, whereas 2 consists of 2D [RbBiS] polyanionic slabs stacked

  15. Structure of a Multilayer Nanofilm To Increase the Encapsulation Efficiency of Basic Fibroblast Growth Factor.

    Science.gov (United States)

    Han, Uiyoung; Hong, Jinkee

    2018-03-05

    In this study, we established the structure of a multilayer nanofilm that more efficiently encapsulates basic fibroblast growth factor (bFGF). First, a positively charged layer material was selected from biocompatible polymers such as collagen (Col), poly(beta-amino ester) (Poly2), and chitosan (Chi), while considering the film thickness. We then investigated the change in bFGF encapsulation efficiency when the multilayer structure was changed from a tetralayer to a trilayer. As a result, we obtained a highly improved bFGF encapsulation efficiency in the nanofilm using a positively charged layer formed by a blend of Col and Poly2 and a negatively charged poly(acrylic acid) (PAA) layer within a trilayered structure. In particular, we found that a significant amount of adsorbed bFGF was desorbed again during the film fabrication process of a tetralayered nanofilm. In the conventional nanofilm, bFGF was regarded as a polycation and formed a multilayer nanofilm that was composed of a tetralayered structure and was represented as (polycation/polyanion/bFGF/polyanion) n where n = number of repeated tetralayers. Here, we suggested that bFGF should not be considered a polycation, rather it should be considered as a small quantity of molecule that exists between the polyanion and polycation layers. In this case, the nanofilm is composed of repeating units of (polycation/polyanion/bFGF/polycation/polyanion), because the amount of adsorbed bFGF is considerably lower than that of other building blocks.

  16. Review and Evaluation of Army Aviation Depot NDI (Nondestructive Inspection) and Reliability Centered Maintenance

    Science.gov (United States)

    1988-08-31

    TAILBOOM ATTACH FITTINC UPPER & LOWER RH 2n _3 S C Y J D U R FUELL CELL AFT BULKHEAD PANEl. R/H Ib 54 S C Y J D U R FUEL CELL UPPER OUTBOARD PANEL R/H...in the real world. terns i-n tnis cIass are generally simple (so-called "sg- cell ") components such as tarts wich are subject to metal ’atizue or otner...AH-64 airframe, the automated airframe logbooK, the upgraded RCA data base management system, the ACE/AACE, CFD, PEM , breakout and other programs as

  17. On the irrationality measure for a q-analogue of \\zeta(2)

    Science.gov (United States)

    Zudilin, W. V.

    2002-08-01

    A Liouville-type estimate is proved for the irrationality measure of the quantities \\displaystyle \\zeta_q(2)=\\sum_{n=1}^\\infty\\frac{q^n}{(1-q^n)^2}with q^{-1}\\in\\mathbb Z\\setminus\\{0,\\pm1\\}. The proof is based on the application of a q-analogue of the arithmetic method developed by Chudnovsky, Rukhadze, and Hata and of the transformation group for hypergeometric series-the group-structure approach introduced by Rhin and Viola.

  18. 15 local climate-energy plans: regions and districts, local leaders of the struggle against climate change

    International Nuclear Information System (INIS)

    2009-01-01

    This report presents some general information, the sectors addressed by the Climate - Energy Plan, the approaches adopted, the plan elaboration process (organisation, participation and governance, diagnosis and challenges identification, communication actions), the actions and their follow-up, the success factors and the improvement opportunities of the Climate-energy Plans elaborated and adopted by different French regions (Alsace, Aquitaine, Basse-Normandie, Champagne-Ardenne, Franche-Comte, Haute-Normandie, Languedoc-Roussillon, Limousin, Nord-Pas-de-Calais, Poitou-Charentes) and districts (Alpes Maritimes, Bas-Rhin, Eure, Seine-Maritime)

  19. Steering committee for the management of the post-accidental phase of a nuclear accident or of a radiological situation (CODIRPA). Validated report of the 'Public reception and information Centre' work group - December 2011. Work document

    International Nuclear Information System (INIS)

    2011-12-01

    As previous works performed by the CODIRPA proposed the creation of Centres for public reception and information (CAIs) within the population protection area, and as local groups have been created in three districts (Vienne, Haut-Rhin, Drome) to work on the preparation of the implementation of such centres, this report proposes a synthesis of these previous works, examines the doctrine related to the support to victims of collective accidents by the ministry of interior and by the ministry of justice, and finally makes recommendations and proposals for the implementation of CAIs in a post-accidental situation

  20. Sequence similarity between the erythrocyte binding domain of the Plasmodium vivax Duffy binding protein and the V3 loop of HIV-1 strain MN reveals a functional heparin binding motif involved in binding to the Duffy antigen receptor for chemokines

    OpenAIRE

    Bolton, Michael J; Garry, Robert F

    2011-01-01

    Abstract Background The HIV surface glycoprotein gp120 (SU, gp120) and the Plasmodium vivax Duffy binding protein (PvDBP) bind to chemokine receptors during infection and have a site of amino acid sequence similarity in their binding domains that often includes a heparin binding motif (HBM). Infection by either pathogen has been found to be inhibited by polyanions. Results Specific polyanions that inhibit HIV infection and bind to the V3 loop of X4 strains also inhibited DBP-mediated infectio...

  1. FORMATION AND ELECTROCHEMICAL BEHAVIOUR OF POLYION COMPLEXES FOR ELECTROCHROMIC DISPLAY MATERIAL

    Institute of Scientific and Technical Information of China (English)

    WAN Guoxiang; WANG Bing; DENG Zhenghua; LUO Chunqiao

    1988-01-01

    Formation of intermacromolecular complexes containing viologen and electron-transfer reaction occurred on the electrode modified by the complex films were studied. Compositions and morphology of the complexes depend on the properties of polyanion and chemical environment of complexation. The analytical results of cyclic voltammetry (CV) and rotating disk voltammetry(RDV) indicated: (1) active sites of viologen in network of complexes transferred single electron reversibly; (2) the redox peak currents showed excellent symmetry and stability; (3) redox potentials were related to properties of polyanions, varying from -0.4 to -0.6V (vs. SCE). Electrochromic materials with different displaying colors could be obtained by changing the structure of polyviologen.

  2. Reduction in Friction and Wear of Alumina Surfaces as Assisted with Surface-Adsorbing Polymers in Aqueous Solutions

    DEFF Research Database (Denmark)

    Røn, Troels; Lee, Seunghwan

    2016-01-01

    We have investigated the aqueous lubricating effects of various polymers for the sliding contacts of self-mated alumina surfaces in neutral aqueous environment. Given that isoelectric point (IEP) of alumina is ca. pH 9, polyanions can readily adsorb onto alumina surface at neutral pH via electros......We have investigated the aqueous lubricating effects of various polymers for the sliding contacts of self-mated alumina surfaces in neutral aqueous environment. Given that isoelectric point (IEP) of alumina is ca. pH 9, polyanions can readily adsorb onto alumina surface at neutral pH via...

  3. Reflections on the role of open source in health information system interoperability.

    Science.gov (United States)

    Sfakianakis, S; Chronaki, C E; Chiarugi, F; Conforti, F; Katehakis, D G

    2007-01-01

    This paper reflects on the role of open source in health information system interoperability. Open source is a driving force in computer science research and the development of information systems. It facilitates the sharing of information and ideas, enables evolutionary development and open collaborative testing of code, and broadens the adoption of interoperability standards. In health care, information systems have been developed largely ad hoc following proprietary specifications and customized design. However, the wide deployment of integrated services such as Electronic Health Records (EHRs) over regional health information networks (RHINs) relies on interoperability of the underlying information systems and medical devices. This reflection is built on the experiences of the PICNIC project that developed shared software infrastructure components in open source for RHINs and the OpenECG network that offers open source components to lower the implementation cost of interoperability standards such as SCP-ECG, in electrocardiography. Open source components implementing standards and a community providing feedback from real-world use are key enablers of health care information system interoperability. Investing in open source is investing in interoperability and a vital aspect of a long term strategy towards comprehensive health services and clinical research.

  4. PCR-based approach to SINE isolation: simple and complex SINEs.

    Science.gov (United States)

    Borodulina, Olga R; Kramerov, Dmitri A

    2005-04-11

    Highly repeated copies of short interspersed elements (SINEs) occur in eukaryotic genomes. The distribution of each SINE family is usually restricted to some genera, families, or orders. SINEs have an RNA polymerase III internal promoter, which is composed of boxes A and B. Here we propose a method for isolation of novel SINE families based on genomic DNA PCR with oligonucleotide identical to box A as a primer. Cloning of the size-heterogeneous PCR-products and sequencing of their terminal regions allow determination of SINE structure. Using this approach, two novel SINE families, Rhin-1 and Das-1, from the genomes of great horseshoe bat (Rhinolophus ferrumequinum) and nine-banded armadillo (Dasypus novemcinctus), respectively, were isolated and studied. The distribution of Rhin-1 is restricted to two of six bat families tested. Copies of this SINE are characterized by frequent internal insertions and significant length (200-270 bp). Das-1 being only 90 bp in length is one of the shortest SINEs known. Most of Das-1 nucleotide sequences demonstrate significant similarity to alanine tRNA which appears to be an evolutionary progenitor of this SINE. Together with three other known SINEs (ID, Vic-1, and CYN), Das-1 constitutes a group of simple SINEs. Interestingly, three SINE families of this group are alanine tRNA-derived. Most probably, this tRNA gave rise to short and simple but successful SINEs several times during mammalian evolution.

  5. Visualization maps for the evolution of research hotspots in the field of regional health information networks.

    Science.gov (United States)

    Wang, Yanjun; Zheng, Jianzhong; Zhang, Ailian; Zhou, Wei; Dong, Haiyuan

    2018-03-01

    The aim of this study was to reveal research hotspots in the field of regional health information networks (RHINs) and use visualization techniques to explore their evolution over time and differences between countries. We conducted a literature review for a 50-year period and compared the prevalence of certain index terms during the periods 1963-1993 and 1994-2014 and in six countries. We applied keyword frequency analysis, keyword co-occurrence analysis, multidimensional scaling analysis, and network visualization technology. The total number of keywords was found to increase with time. From 1994 to 2014, the research priorities shifted from hospital planning to community health planning. The number of keywords reflecting information-based research increased. The density of the knowledge network increased significantly, and partial keywords condensed into knowledge groups. All six countries focus on keywords including Information Systems; Telemedicine; Information Service; Medical Records Systems, Computerized; Internet; etc.; however, the level of development and some research priorities are different. RHIN research has generally increased in popularity over the past 50 years. The research hotspots are evolving and are at different levels of development in different countries. Knowledge network mapping and perceptual maps provide useful information for scholars, managers, and policy-makers.

  6. Comparative pharmacokinetic, immunologic and hematologic studies on the anti-HIV-1/2 compounds aconitylated and succinylated HSA

    NARCIS (Netherlands)

    Swart, P J; Beljaars, E; Smit, C; Pasma, A; Schuitemaker, H; Meijer, D K

    1996-01-01

    Charge modification by succinylation or cis-aconitylation of the terminal epsilon NH2 functions of the amino acid lysine in human serum albumin, resulted in polyanionic compounds with an anti-HIV-1 activity in the low nanomolar concentration range. After iv injections in rats of the negatively

  7. CK2: a protein kinase in need of control

    DEFF Research Database (Denmark)

    Guerra, B; Boldyreff, B; Sarno, S

    1999-01-01

    that are responsible for the recognition of phosphoacceptor substrates and for down-regulation by the beta-subunit and by polyanionic inhibitors. The resolution of the crystal structure of Zea mays CK2 alpha-subunit has disclosed the structural features that are responsible for high basal activity and for unusual...

  8. Electrochemical study of two structurally related compounds and ...

    Indian Academy of Sciences (India)

    D Saritha

    2018-02-01

    Feb 1, 2018 ... lysts for selective oxidation of hydrocarbons. Numerous polyanionic ... attracted attention as positive electrodes because of the possibility of using the .... SEM pictures of (a) FeVMoO7, (b) CrVMoO7. the voltage of the cell ...

  9. Cross-linked polyelectrolyte multilayers for marine antifouling applications

    NARCIS (Netherlands)

    Zhu, X.; Janczewski, D.; Lee, S.S.C.; Teo, S.L-M.; Vancso, Gyula J.

    2013-01-01

    A polyionic multilayer film was fabricated by layer-by-layer (LbL) sequential deposition followed by cross-linking under mild conditions on a substrate surface to inhibit marine fouling. A novel polyanion, featuring methyl ester groups for an easy cross-linking was used as a generic solution for

  10. Highly Effective Non-Viral Antitumor Gene Therapy System Comprised of Biocompatible Small Plasmid Complex Particles Consisting of pDNA, Anionic Polysaccharide, and Fully Deprotected Linear Polyethylenimine

    Directory of Open Access Journals (Sweden)

    Yoshiyuki Koyama

    2015-07-01

    Full Text Available We have reported that ternary complexes of plasmid DNA with conventional linear polyethylenimine (l-PEI and certain polyanions were very stably dispersed, and, with no cryoprotectant, they could be freeze-dried and re-hydrated without the loss of transfection ability. These properties enabled the preparation of a concentrated suspension of very small pDNA complex, by preparing the complexes at highly diluted conditions, followed by condensation via lyophilization-and-rehydration procedure. Recently, a high potency linear polyethylenimine having no residual protective groups, i.e., Polyethylenimine “Max” (PEI “Max”, is available, which has been reported to induce much higher gene expression than conventional l-PEI. We tried to prepare the small DNA/PEI “Max”/polyanion complexes by a similar freeze-drying method. Small complex particles could be obtained without apparent aggregation, but transfection activity of the rehydrated complexes was severely reduced. Complex-preparation conditions were investigated in details to achieve the freeze-dried DNA/PEI “Max”/polyanion small ternary complexes with high transfection efficiency. DNA/PEI “Max”/polyanion complexes containing cytokine-coding plasmids were then prepared, and their anti-tumor therapeutic efficacy was examined in tumor-bearing mice.

  11. Electrostatics and Flexibility Drive Membrane Recognition and Early Penetration by Antimicrobial Peptide Dendrimer bH1

    Energy Technology Data Exchange (ETDEWEB)

    Ravi, Harish Kumar; Stach, Michaela; Soares, Thereza A.; Darbre, Tamis; Reymond, Jean-Louis; Cascella, Michele

    2013-08-01

    Molecular dynamics simulation of polycationic antimicrobial peptide dendrimer bH1 (Leu)8(DapLeu)4(DapPhe)2DapLys- NH2 binding to membranes suggest that electrostatic 10 interactions with the polyanionic lipopolysaccharide (LPS) and conformational flexibility of the 2,3-diaminopropanoic acid (Dap) branching units drive its selective insertion into microbial membranes.

  12. Hydrides of Alkaline Earth–Tetrel (AeTt) Zintl Phases: Covalent Tt–H Bonds from Silicon to Tin

    Energy Technology Data Exchange (ETDEWEB)

    Auer, Henry; Guehne, Robin; Bertmer, Marko; Weber, Sebastian; Wenderoth, Patrick; Hansen, Thomas Christian; Haase, Jürgen; Kohlmann, Holger (Leipzig); (Saarland-MED); (ILL)

    2017-01-18

    Zintl phases form hydrides either by incorporating hydride anions (interstitial hydrides) or by covalent bonding of H to the polyanion (polyanionic hydrides), which yields a variety of different compositions and bonding situations. Hydrides (deuterides) of SrGe, BaSi, and BaSn were prepared by hydrogenation (deuteration) of the CrB-type Zintl phases AeTt and characterized by laboratory X-ray, synchrotron, and neutron diffraction, NMR spectroscopy, and quantum-chemical calculations. SrGeD4/3–x and BaSnD4/3–x show condensed boatlike six-membered rings of Tt atoms, formed by joining three of the zigzag chains contained in the Zintl phase. These new polyanionic motifs are terminated by covalently bound H atoms with d(Ge–D) = 1.521(9) Å and d(Sn–D) = 1.858(8) Å. Additional hydride anions are located in Ae4 tetrahedra; thus, the features of both interstitial hydrides and polyanionic hydrides are represented. BaSiD2–x retains the zigzag Si chain as in the parent Zintl phase, but in the hydride (deuteride), it is terminated by H (D) atoms, thus forming a linear (SiD) chain with d(Si–D) = 1.641(5) Å.

  13. Multilayers of Fluorinated Amphiphilic Polyions for Marine Fouling Prevention

    NARCIS (Netherlands)

    Zhu, X.; Guo, S.; Janczewski, D.; Parra-Velandia, F.J.; Teo, S.L-M.; Vancso, Gyula J.

    2014-01-01

    Sequential layer-by-layer (LbL) deposition of polyelectrolytes followed by chemical cross-linking was investigated as a method to fabricate functional amphiphilic surfaces for marine biofouling prevention applications. A novel polyanion, grafted with amphiphilic perfluoroalkyl polyethylene glycol

  14. USE OF WOOD DERIVATIVES AS DOPING / DISPERSING AGENTS IN THE PREPARATION OF POLYPYRROLE AQUEOUS DISPERSIONS

    Directory of Open Access Journals (Sweden)

    Claudia Sasso

    2008-11-01

    Full Text Available Polystyrene sulfonic acid (PSS, lignosulfonic acid (LS sodium salts, and carboxymethylcellulose (CMC were used as doping/dispersing agents in the chemical polymerization of polypyrrole (Ppy. Conductivity measure-ments performed on dry Ppy pellets showed a sharp increase in conductivity when adding the anionic polymers to the polymerization liquor. For a polyanion/pyrrole weight ratio ranging between 0.1 and 0.6, the highest conductivity was given by PpyCMC (82 S/m and PpyPSS (80 S/m, followed by PpyLS (6 S/m. On the other hand, for a polyanion/pyrrole ratio higher than 0.6, the conductivity of PpyPSS systems sharply decreased, and for polyanion/pyrrole ratios higher than 1, the highest conductivity was given by PpyCMC (~10 S/m, followed by PpyLS (~7 S/m and PpyPSS (~5 S/m. Zeta-potential measurements showed that the surface charge of Ppy was strongly affected by the polyanion type and amount. Cationic Ppy particles were obtained in the presence of the two polymers bearing strongly acidic moieties (PSS and LS. Anionic PpyPSS colloids were obtained at the highest PSS/Py ratio, after the degradation of the conducting properties. When using a weakly acidic dopant (CMC, PpyCMC colloids had a negative charge for all of the tested conditions.

  15. Studies on protein synthesis by protoplasts of Saccharomyces carlsbergensis II. Reversal of the RNase effect of protein synthesis by polymethacrylic acid

    NARCIS (Netherlands)

    Kloet, S.R. de; Wermeskerken, R.K.A. van; Koningsberger, V.V.

    1961-01-01

    The ribonuclease inhibited protein synthesis and respiration of yeast protoplasts can be restored by the addition of several polyanionic compounds, among which polymethacrylic acid proved to be the most effective one. The results of preliminary experiments with the ultracentrifuge indicate a

  16. Cuprolinic Blue: a specific dye for single-stranded RNA in the presence of magnesium chloride. I. Fundamental aspects

    NARCIS (Netherlands)

    Tas, J.; MENDELSON, D.; NOORDEN, C. J. F.

    1983-01-01

    Qualitative and quantitative aspects of the cationic dye Cuprolinic Blue were investigated with model films of polyacrylamide gel in which RNA, DNA and other biological polyanionic compounds had been incorporated. In the presence of 1 M MgCl2, Curpolinic Blue was found to bind specifically to

  17. Delivering a lifelong integrated electronic health record based on a service oriented architecture.

    Science.gov (United States)

    Katehakis, Dimitrios G; Sfakianakis, Stelios G; Kavlentakis, Georgios; Anthoulakis, Dimitrios N; Tsiknakis, Manolis

    2007-11-01

    Efficient access to a citizen's Integrated Electronic Health Record (I-EHR) is considered to be the cornerstone for the support of continuity of care, the reduction of avoidable mistakes, and the provision of tools and methods to support evidence-based medicine. For the past several years, a number of applications and services (including a lifelong I-EHR) have been installed, and enterprise and regional infrastructure has been developed, in HYGEIAnet, the Regional Health Information Network (RHIN) of the island of Crete, Greece. Through this paper, the technological effort toward the delivery of a lifelong I-EHR by means of World Wide Web Consortium (W3C) technologies, on top of a service-oriented architecture that reuses already existing middleware components is presented and critical issues are discussed. Certain design and development decisions are exposed and explained, laying this way the ground for coordinated, dynamic navigation to personalized healthcare delivery.

  18. Deep geothermal energy: the Soultz-sous-Forets experience

    International Nuclear Information System (INIS)

    Genter, A.; Guenot, N.; Graff, J.J.

    2010-01-01

    This paper presents the mining exploitation project of the geothermal heat at Soultz-sous-Forets, located 50 km NE of Strasbourg (Bas Rhin, France). A geothermal power plant, inaugurated mid-2008, will commercialize its own power generation soon. This power plant is owned by a consortium of French-German industrialists through the European economical interest group for the mining exploitation of heat. The paper presents the geological characteristics of the hot dry rock geothermal reservoir, the deep geothermal wells, the hydraulic stimulation of the reservoir rock, the surface equipments of the power plants and the production pumps, the activities of the site in 2008 and 2009 and the perspectives of development of this energy source in France in the light of the Soultz-sous-Forets site experience. (J.S.)

  19. The largest Fresco in Europe on cooling tower of nuclear power station of Cruas Meysse in Ardeche, France

    International Nuclear Information System (INIS)

    Di Mayo, J.L.

    1993-01-01

    The Nuclear Power Station Cruas Meysse is on the most important communication way of France, in the Rhone Valley, between the Rhin and the Mediterranean Sea. In the South of the Rhone Valley, the Nuclear Power Plant is situated near the very important site of 'Tricastin', the largest nuclear area in France. Cruas Meysse has a very good integration to the economy, social, and cultural scheme ; that's why EDF and the Ardeche Department had enter into partnership to associate art and technology of our time, and offer a work for everybody - 'Le Verseau' is the largest fresco in Europe - It gives a gigantic signalling system to the Ardeche Department, because the Nuclear Power Station has a very interesting position, close the motor way A7, the National 7 road, and the way of high speed train (TGV) an another symbol of the high French technology

  20. L’INVASION DU RÉSEAU HYDROGRAPHIQUE FRANÇAIS PAR LES MOLLUSQUES CORBICULA SPP. MODALITÉ DE COLONISATION ET RÔLE PRÉPONDÉRANT DES CANAUX DE NAVIGATION.

    Directory of Open Access Journals (Sweden)

    BRANCOTTE V.

    2002-04-01

    Full Text Available Originaire d’Asie et d’Afrique, Corbicula a colonisé la plupart des bassins hydrographiques européens depuis 1980. A la faveur de la découverte de nouvelles stations, les auteurs mettent en évidence l’importance du rôle des canaux de navigation dans la propagation du mollusque, par la mise en connexion des bassins versants et l’existence d’un milieu particulièrement favorable à la biologie de l’espèce. Corbicula a pénétré en France par au moins sept axes différents, parmi lesquels le Rhin joue un rôle prépondérant.

  1. Arraisonner la divinité ? Limites religieuses de la pensée technique

    OpenAIRE

    Svenbro, Jesper

    2017-01-01

    Dans une enquête sur les tekhnai en Grèce ancienne, l’évocation de la conférence de Martin Heidegger sur La pensée technique (1953) peut sans doute apparaître comme un hors-sujet, d’autant plus que l’un de ses concepts-clé, l’« arraisonnement », ne concernerait que le monde moderne. Ainsi, selon Heidegger, le Rhin se trouve « arraisonné », c’est-à-dire sommé de livrer son énergie à la centrale hydro-électrique dans laquelle il est muré. À titre contrastif et expérimental, on a voulu confronte...

  2. La monarquía sueva en el s. V. Aspectos políticos y prosopográficos

    Directory of Open Access Journals (Sweden)

    Pablo C. DÍAZ MARTÍNEZ

    2010-02-01

    Full Text Available La monarquía sueva de Hispania fue la primera que como tal organizó un reino independiente y territorialmente asentado en los límites del Imperio Romano. A partir de los años 409-411 los suevos aparecen instalados en los límites occidentales de la provincia Gallaecia 1. Durante casi dos siglos sobrevivirán a aquellos pueblos que habían atravesado con ellos el Rhin en el 406, a los restos del poder imperial en occidente y, durante todo este periodo, serán capaces de hacer frente, con mayor o menos fortuna, al expansionismo creciente de los visigodos.

  3. Radiation Mitigation and Power Optimization Design Tools for Reconfigurable Hardware in Orbit

    Science.gov (United States)

    French, Matthew; Graham, Paul; Wirthlin, Michael; Wang, Li; Larchev, Gregory

    2005-01-01

    The Reconfigurable Hardware in Orbit (RHinO)project is focused on creating a set of design tools that facilitate and automate design techniques for reconfigurable computing in space, using SRAM-based field-programmable-gate-array (FPGA) technology. In the second year of the project, design tools that leverage an established FPGA design environment have been created to visualize and analyze an FPGA circuit for radiation weaknesses and power inefficiencies. For radiation, a single event Upset (SEU) emulator, persistence analysis tool, and a half-latch removal tool for Xilinx/Virtex-II devices have been created. Research is underway on a persistence mitigation tool and multiple bit upsets (MBU) studies. For power, synthesis level dynamic power visualization and analysis tools have been completed. Power optimization tools are under development and preliminary test results are positive.

  4. Liminaire

    OpenAIRE

    Husson, Laurent; Seydoux, Guillaume

    2008-01-01

    Le Portique ne pouvait rester indifférent au centenaire de la nais­sance de Sartre. Six philosophes des deux côtés du Rhin, Manfred Frank (Tübingen), Guillaume Seydoux (Metz), Jean-Christophe Merle (Tours et Saarbrücken), Laurent Husson (Metz), Alain Flajo­liet (Paris) et Gerhard Seel (Berne) ont interrogé sa pensée philoso­phique à partir de ses fonde­ments ontologiques et de ses perspectives morales. La théorie sartrienne de la conscience, éclairée dans sa singula­rité à l’aide des traditi...

  5. Gallium(III)-Containing, Sandwich-Type Heteropolytungstates: Synthesis, Solution Characterization, and Hydrolytic Studies toward Phosphoester and Phosphoanhydride Bond Cleavage.

    Science.gov (United States)

    Kandasamy, Balamurugan; Vanhaecht, Stef; Nkala, Fiona Marylyn; Beelen, Tessa; Bassil, Bassem S; Parac-Vogt, Tatjana N; Kortz, Ulrich

    2016-09-19

    The gallium(III)-containing heteropolytungstates [Ga4(H2O)10(β-XW9O33)2](6-) (X = As(III), 1; Sb(III), 2) were synthesized in aqueous acidic medium by reaction of Ga(3+) ions with the trilacunary, lone-pair-containing [XW9O33](9-). Polyanions 1 and 2 are isostructural and crystallized as the hydrated sodium salts Na6[Ga4(H2O)10(β-AsW9O33)2]·28H2O (Na-1) and Na6[Ga4(H2O)10(β-SbW9O33)2]·30H2O (Na-2) in the monoclinic space group P21/c, with unit cell parameters a = 16.0218(12) Å, b = 15.2044(10) Å, c = 20.0821(12) Å, and β = 95.82(0)°, as well as a = 16.0912(5) Å, b = 15.2178(5) Å, c = 20.1047(5) Å, and β = 96.2(0)°, respectively. The corresponding tellurium(IV) derivative [Ga4(H2O)10(β-TeW9O33)2](4-) (3) was also prepared, by direct reaction of sodium tungstate, tellurium(IV) oxide, and gallium nitrate. Polyanion 3 crystallized as the mixed rubidium/sodium salt Rb2Na2[Ga4(H2O)10(β-TeW9O33)2]·28H2O (RbNa-3) in the triclinic space group P1̅ with unit cell parameters a = 12.5629(15) Å, b = 13.2208(18) Å, c = 15.474(2) Å, α = 80.52(1)°, β = 84.37(1)°, and γ = 65.83(1)°. All polyanions 1-3 were characterized in the solid state by single-crystal XRD, FT-IR, TGA, and elemental analysis, and polyanion 2 was also characterized in solution by (183)W NMR and UV-vis spectroscopy. Polyanion 2 was used as a homogeneous catalyst toward adenosine triphosphate (ATP) and the DNA model substrate 4-nitrophenylphosphate, monitored by (1)H and (31)P NMR spectroscopy. The encapsulated gallium(III) centers in 2 promote the Lewis acidic synergistic activation of the hydrolysis of ATP and DNA model substrates at a higher rate in near-physiological conditions. A strong interaction of 2 with the P-O bond of ATP was evidenced by changes in chemical shift values and line broadening of the (31)P nucleus in ATP upon addition of the polyanion.

  6. L'amministrazione dei culti in Francia

    Directory of Open Access Journals (Sweden)

    Anna Sammassimo

    2013-10-01

    Full Text Available Contributo sottoposto a valutazioneSOMMARIO: 1. Introduzione - 2. La Francia e l’amministrazione dei culti - 3. Le bureau central des cultes: 3.1 - Le origini: dal Consolato al periodo imperiale; 3.2 - dalla Prima alla Seconda Restaurazione; 3.3 - dalla Monarchia di luglio alla Legge sulla separazione; 3.4 - le competenze - 4. Le bureau des cultes des départements du Bas-Rhin, du Haut-Rhin et de la Moselle: 4.1 - la specificità dell’Alsazia-Mosella; 4.2 - le origini del bureau; 4.3 - le competenze - 5. Il conseiller pour les affaires religieuses: 5.1 - le origini; 5.2 - la posizione fuori dagli schemi; 5.3 - le competenze – 6. Conclusioni.  Abstract:The administration of cults in FranceThe expression “Administration of cults” born in France in the 19th century, when the 1801 Conordat made the cults into a public service and the cult's clerics a corp of nominated functionaries. Thus administration referred precisely to that branch of the civil service which under the flourishing Concordat concerned itself with the problems of claims from and requirements of the religious cults in French territories. Our paper means to trace France's administration of cults from its beginnings to its precise modern competences and functions. We wish to show how this administrative structure has been and still is an important apparatus for interpretation and even for 'liberal administration' of the Law as regards the separation of State and Church and the very concept of laïcité.Key words: France, administration, cults, laïcité

  7. Lipoplex size is a major determinant of in vitro lipofection efficiency.

    Science.gov (United States)

    Ross, P C; Hui, S W

    1999-04-01

    The inhibition effect of serum on the transfection efficiency of cationic liposome-DNA complexes (lipoplexes) is a major obstacle to the application of this gene delivery vector both in vitro and in vivo. The size of the lipoplexes, as they are presented to targeted cells, is found to be the major determinant of their effectiveness in transfection. The transfection efficiency and the cell association and uptake of lipoplexes with CHO cells was found to increase with increasing lipoplex size. The influence on the transfection efficiency of lipoplexes by their cationic lipid:DNA ratios, types of liposomes, incubation time in polyanion containing media, and time of serum addition, are mediated mainly through size. Lipoplexes at a 2:1 charge ratio grow in size in media containing polyanions. The size growth may be arrested by adding serum to the incubation media. By using large lipoplexes, especially those made from multilamellar vesicles, the serum inhibition effect may be overcome.

  8. Crystal structure of catena-poly[N,N,N′,N′-tetramethylguanidinium [(chloridocadmate-di-μ-chlorido

    Directory of Open Access Journals (Sweden)

    Mamadou Ndiaye

    2016-01-01

    Full Text Available In the structure of the title salt, {(C5H14N3[CdCl3]}n, the CdII atom of the complex anion is five-coordinated by one terminal and four bridging Cl atoms. The corresponding coordination polyhedron is a distorted trigonal bipyramid, with Cd—Cl distances in the range 2.4829 (4–2.6402 (4 Å. The bipyramids are condensed into a polyanionic zigzag chain extending parallel to [101]. The tetramethylguanidinium cations are situated between the polyanionic chains and are linked to them through N—H...Cl hydrogen bonds, forming a layered network parallel to (010.

  9. Oligonucleotides as probes for studying polymerization reactions in dilute aqueous solution

    Science.gov (United States)

    Kolb, V.; Orgel, L. E.; Miller, S. L. (Principal Investigator)

    1994-01-01

    We have prepared a [32P]-labled oligonucleotide probe carrying a free primary amine at its 3'-terminus. This probe is used to initiate polymerization of aziridine (ethyleneimine) in aqueous solution. The nature of the oligomeric products and the kinetics of their formation are then monitored by gel electrophoresis. Our results are generally consistent with those obtained using conventional techniques. We have also investigated the effect of polyanionic templates on the rate of oligomerization of aziridine. We find that water-soluble polyanions generally accelerate the polymerization. The sodium salt of polymethacrylic acid is the most effective of the templates that we studied. The methods introduced in this paper should be applicable to a variety of polymerization reactions in aqueous solution. They should greatly simplify the screening of potentially prebiotic polymerization reactions.

  10. Nanocaged enzymes with enhanced catalytic activity and increased stability against protease digestion

    Science.gov (United States)

    Zhao, Zhao; Fu, Jinglin; Dhakal, Soma; Johnson-Buck, Alexander; Liu, Minghui; Zhang, Ting; Woodbury, Neal W.; Liu, Yan; Walter, Nils G.; Yan, Hao

    2016-01-01

    Cells routinely compartmentalize enzymes for enhanced efficiency of their metabolic pathways. Here we report a general approach to construct DNA nanocaged enzymes for enhancing catalytic activity and stability. Nanocaged enzymes are realized by self-assembly into DNA nanocages with well-controlled stoichiometry and architecture that enabled a systematic study of the impact of both encapsulation and proximal polyanionic surfaces on a set of common metabolic enzymes. Activity assays at both bulk and single-molecule levels demonstrate increased substrate turnover numbers for DNA nanocage-encapsulated enzymes. Unexpectedly, we observe a significant inverse correlation between the size of a protein and its activity enhancement. This effect is consistent with a model wherein distal polyanionic surfaces of the nanocage enhance the stability of active enzyme conformations through the action of a strongly bound hydration layer. We further show that DNA nanocages protect encapsulated enzymes against proteases, demonstrating their practical utility in functional biomaterials and biotechnology. PMID:26861509

  11. Nanocaged enzymes with enhanced catalytic activity and increased stability against protease digestion

    Science.gov (United States)

    Zhao, Zhao; Fu, Jinglin; Dhakal, Soma; Johnson-Buck, Alexander; Liu, Minghui; Zhang, Ting; Woodbury, Neal W.; Liu, Yan; Walter, Nils G.; Yan, Hao

    2016-02-01

    Cells routinely compartmentalize enzymes for enhanced efficiency of their metabolic pathways. Here we report a general approach to construct DNA nanocaged enzymes for enhancing catalytic activity and stability. Nanocaged enzymes are realized by self-assembly into DNA nanocages with well-controlled stoichiometry and architecture that enabled a systematic study of the impact of both encapsulation and proximal polyanionic surfaces on a set of common metabolic enzymes. Activity assays at both bulk and single-molecule levels demonstrate increased substrate turnover numbers for DNA nanocage-encapsulated enzymes. Unexpectedly, we observe a significant inverse correlation between the size of a protein and its activity enhancement. This effect is consistent with a model wherein distal polyanionic surfaces of the nanocage enhance the stability of active enzyme conformations through the action of a strongly bound hydration layer. We further show that DNA nanocages protect encapsulated enzymes against proteases, demonstrating their practical utility in functional biomaterials and biotechnology.

  12. Lipid Phases Eye View to Lipofection. Cationic Phosphatidylcholine Derivatives as Efficient DNA Carriers for Gene Delivery

    OpenAIRE

    Rumiana Koynova

    2008-01-01

    Efficient delivery of genetic material to cells is needed for tasks of utmost importance in laboratory and clinic, such as gene transfection and gene silencing. Synthetic cationic lipids can be used as delivery vehicles for nucleic acids and are now considered the most promising non-viral gene carriers. They form complexes (lipoplexes) with the polyanionic nucleic acids. A critical obstacle for clinical application of the lipid-mediated DNA delivery (lipofection) is its unsatisfactory efficie...

  13. Design of Chitosan and Its Water Soluble Derivatives-Based Drug Carriers with Polyelectrolyte Complexes

    OpenAIRE

    Wu, Qing-Xi; Lin, Dong-Qiang; Yao, Shan-Jing

    2014-01-01

    Chitosan, the cationic polysaccharide derived from the natural polysaccharide chitin, has been studied as a biomaterial for more than two decades. As a polycationic polymer with favorable properties, it has been widely used to form polyelectrolyte complexes with polyanions for various applications in drug delivery fields. In recent years, a growing number of studies have been focused on the preparation of polyelectrolyte complexes based on chitosan and its water soluble derivatives. They have...

  14. Gulf of Mexico mud toxicity limitations

    Energy Technology Data Exchange (ETDEWEB)

    Dunn, H.E.; Beardmore, D.H. (Phillips Petroleum Co., Bartlesville, OK (USA)); Stewart, W.S. (Drilling Specialties Co. (US))

    1989-10-01

    Because of the Environmental Protection Agency's recent toxicity limits on drilling mud discharges for offshore Gulf of Mexico, Phillips Petroleum conducted a mud toxicity study based on both field and lab tests. The study, discussed in this article, found the polyanionic cellulose-sulfomethylated quebracho-chrome lignosulfonate mud Phillips had been using would comfortably pass the toxicity limitations. The study also found barite and thinners were of low toxicity, and hydrocarbons and surfactants were highly toxic.

  15. Imprinting of metal receptors into multilayer polyelectrolyte films: fabrication and applications in marine antifouling

    OpenAIRE

    Puniredd, S.R.; Janczewski, D.; Go, D.P.; Zhu, X.; Guo, S.; Teo, S.L-M.; Lee, S.S.C.; Vancso, Gyula J.

    2015-01-01

    Polymeric films constructed using the layer-by-layer (LbL) fabrication process were employed as a platform for metal ion immobilization and applied as a marine antifouling coating. The novel Cu2+ ion imprinting process described is based on the use of metal ion templates and LbL multilayer covalent cross-linking. Custom synthesized, peptide mimicking polycations composed of histidine grafted poly(allylamine) (PAH) to bind metal ions, and methyl ester containing polyanions for convenient cross...

  16. Application of extraction of gallium molybdotungstate HPA for their investigation in solutions and gallium determination

    International Nuclear Information System (INIS)

    Kol'tsova, E.G.; Vakulich, A.N.; Tsyganok, L.P.

    2001-01-01

    Extraction of gallium molybdotungstate heteropolyacids and their associates with a row of triphenylmethane dyes, use of extraction for study of complexing in Mo 6 -W 6 -Ga 3+ -H 3 O + system are investigated. Research of optimal analytical states and development of extraction spectrophotometric methods of gallium determination are done. It is shown that increase of Mo 6 part in heteropolyanion improves solvation interaction of heteropolyacids with organic solvents elevating extraction properties of polyanion [ru

  17. The effect of polymer charge density and charge distribution on the formation of multilayers

    CERN Document Server

    Voigt, U; Tauer, K; Hahn, M; Jäger, W; Klitzing, K V

    2003-01-01

    Polyelectrolyte multilayers which are built up by alternating adsorption of polyanions and polycations from aqueous solutions at a solid interface are investigated by reflectometry and ellipsometry. Below a degree of charge of about 70% the adsorption stops after a certain number of dipping cycles and no multilayer formation occurs. This indicates an electrostatically driven adsorption process. Below a charge density of 70% an adsorption can take place if the charged segments are combined as a block of the polymer.

  18. Towards Liquid Chromatography Time-Scale Peptide Sequencing and Characterization of Post-Translational Modifications in the Negative-Ion Mode Using Electron Detachment Dissociation Tandem Mass Spectrometry

    DEFF Research Database (Denmark)

    Kjeldsen, Frank; Hørning, Ole B; Jensen, Søren S

    2008-01-01

    Electron detachment dissociation (EDD) of peptide poly-anions is gentle towards post-translational modifications (PTMs) and produces predictable and interpretable fragment ion types (a., x ions). However, EDD is considered an inefficient fragmentation technique and has not yet been implemented...... coverage and extended PTM characterization the new regime of EDD in combination with other ion-electron fragmentation techniques in the positive-ion mode is a step towards a more comprehensive strategy of analysis in proteome research....

  19. Synthesis and electrochemical analysis of AlVMoO7 oxide prepared ...

    Indian Academy of Sciences (India)

    2018-05-16

    May 16, 2018 ... solid solution and two-phase regimes. In the voltage ... LiMn2O4) [1]. Among these compounds, olivine LiFePO4, ... polyanions provide numerous metal oxidation states, struc- tural stability ... 2.1a Sol–gel synthesis (SG): In SG synthesis method, ... AlVMoO7 and confirms that only a single phase is formed.

  20. Conduction Mechanisms and Structure of Ionomeric Single-Ion Conductors

    Energy Technology Data Exchange (ETDEWEB)

    Colby, Ralph H. [Pennsylvania State Univ., University Park, PA (United States); Maranas, Janna K. [Pennsylvania State Univ., University Park, PA (United States); Mueller, Karl T. [Pennsylvania State Univ., University Park, PA (United States); Runt, James [Pennsylvania State Univ., University Park, PA (United States); Winey, Karen I. [Univ. of Pennsylvania, Philadelphia, PA (United States)

    2015-03-01

    Our team has designed using DFT (Gaussian) and synthesized low glass transition temperature single-ion conductors that are either polyanions that conduct small cations Li+, Na+, Cs+ or polycations that conduct small anions F-, OH-, Br-. We utilize a wide range of complimentary experimental materials characterization tools to understand ion transport; differential scanning calorimetry, dielectric relaxation spectroscopy, infrared spectroscopy, nuclear magnetic resonance spectroscopy, linear viscoelasticity, X-ray scattering and molecular dynamics simulations. The glass transition temperature Tg needs to be as low as possible to facilitate ion transport, so the nonionic parts of the polymer need to be polar, flexible and have strong solvation interactions with the ions. The lowest Tg we have managed for polyanions conducting Li+ is -60 °C. In contrast, polysiloxanes with PEO side chains and tetrabutylphosphonium cationic side groups have Tg ≈ -75 °C that barely increases with ion content, as anticipated by DFT. A survey of all polyanions in the literature suggests that Tg < -80 °C is needed to achieve the 10-4 S/cm conductivity needed for battery separators.

  1. Nozzleless Fabrication of Oil-Core Biopolymeric Microcapsules by the Interfacial Gelation of Pickering Emulsion Templates.

    Science.gov (United States)

    Leong, Jun-Yee; Tey, Beng-Ti; Tan, Chin-Ping; Chan, Eng-Seng

    2015-08-05

    Ionotropic gelation has been an attractive method for the fabrication of biopolymeric oil-core microcapsules due to its safe and mild processing conditions. However, the mandatory use of a nozzle system to form the microcapsules restricts the process scalability and the production of small microcapsules (microcapsules through ionotropic gelation at the interface of an O/W Pickering emulsion. This approach involves the self-assembly of calcium carbonate (CaCO3) nanoparticles at the interface of O/W emulsion droplets followed by the addition of a polyanionic biopolymer into the aqueous phase. Subsequently, CaCO3 nanoparticles are dissolved by pH reduction, thus liberating Ca(2+) ions to cross-link the surrounding polyanionic biopolymer to form a shell that encapsulates the oil droplet. We demonstrate the versatility of this method by fabricating microcapsules from different types of polyanionic biopolymers (i.e., alginate, pectin, and gellan gum) and water-immiscible liquid cores (i.e., palm olein, cyclohexane, dichloromethane, and toluene). In addition, small microcapsules with a mean size smaller than 100 μm can be produced by selecting the appropriate conventional emulsification methods available to prepare the Pickering emulsion. The simplicity and versatility of this method allows biopolymeric microcapsules to be fabricated with ease by ionotropic gelation for numerous applications.

  2. Die Veränderung der Grenzen in einer transnationalen Gebietskörperschaft

    Directory of Open Access Journals (Sweden)

    Karen Denni

    2009-12-01

    Full Text Available L’objet de notre article est de mettre en lumière la multiplicité des frontières qui structurent la zone frontalière de Strasbourg-Ortenau. Au cours de son histoire, la frontière francoallemande a considérablement évolué. Zone conflictuelle de rupture comme lors de la guerre franco-allemande de 1870-1871, elle représente désormais un espace pacifié et intégré dans un ensemble politique européen plus large. La convention pour la création d’un eurodistrict franco-allemand conclue en 2005 prévoit même le dépassement des frontières politiques et administratives en visant la fusion de ces deux collectivités contiguës séparées par le Rhin et concourt, grâce à la proximité géographique et organisationnelle que permet la petite structure ainsi créée, à faciliter l’articulation entre l’échelle locale et l’échelle globale. Mais, malgré cette convention qui a intensifié la coopération transfrontalière, ce projet suscite encore de nombreuses interrogations aux plans juridique, politique et social. En outre, les citoyens français et allemands de la zone du Rhin supérieur restent finalement assez peu informés de l’importante progression que connaît la coopération transfrontalière dans ce secteur et n’y voient que peu d’avantages. Une plus large implication des citoyens à ce projet semble indispensable afin que ceux-ci apportent créativité et dynamisme à la construction d’une nouvelle entité politique dans laquelle il leur sera alors possible de s’identifier. Un long chemin reste donc à parcourir avant que le Rhin cesse de représenter une frontière entre la France et l’Allemagne et se transforme en un véritable trait d’union entre ces deux pays.Ziel dieses Artikels ist es, die vielfältigen Aspekte der Grenzen darzulegen, die den Grenzraum Straßburg-Kehl strukturieren. Im Laufe ihrer Geschichte hat die deutsch-französische Grenze einen großen Wandel vollzogen, von einer

  3. Sequence similarity between the erythrocyte binding domain of the Plasmodium vivax Duffy binding protein and the V3 loop of HIV-1 strain MN reveals a functional heparin binding motif involved in binding to the Duffy antigen receptor for chemokines

    Directory of Open Access Journals (Sweden)

    Bolton Michael J

    2011-11-01

    Full Text Available Abstract Background The HIV surface glycoprotein gp120 (SU, gp120 and the Plasmodium vivax Duffy binding protein (PvDBP bind to chemokine receptors during infection and have a site of amino acid sequence similarity in their binding domains that often includes a heparin binding motif (HBM. Infection by either pathogen has been found to be inhibited by polyanions. Results Specific polyanions that inhibit HIV infection and bind to the V3 loop of X4 strains also inhibited DBP-mediated infection of erythrocytes and DBP binding to the Duffy Antigen Receptor for Chemokines (DARC. A peptide including the HBM of PvDBP had similar affinity for heparin as RANTES and V3 loop peptides, and could be specifically inhibited from heparin binding by the same polyanions that inhibit DBP binding to DARC. However, some V3 peptides can competitively inhibit RANTES binding to heparin, but not the PvDBP HBM peptide. Three other members of the DBP family have an HBM sequence that is necessary for erythrocyte binding, however only the protein which binds to DARC, the P. knowlesi alpha protein, is inhibited by heparin from binding to erythrocytes. Heparitinase digestion does not affect the binding of DBP to erythrocytes. Conclusion The HBMs of DBPs that bind to DARC have similar heparin binding affinities as some V3 loop peptides and chemokines, are responsible for specific sulfated polysaccharide inhibition of parasite binding and invasion of red blood cells, and are more likely to bind to negative charges on the receptor than cell surface glycosaminoglycans.

  4. Mineralogy and rheology of raw and activated Turonian to Coniacian clays from Benue Trough, northeastern Nigeria

    Directory of Open Access Journals (Sweden)

    A.S. Arabi

    2018-03-01

    Full Text Available Since the discovery of oil and gas in Oloibiri, an onshore oilfield located in Oloibiri in Ogbia Local Government Area of Bayelsa State, Nigeria on Sunday 15th January 1956 by Shell Darcy, hundreds of oil wells have been drilled and not a single of these oil wells was drilled without the use of bentonite. This work is aimed at evaluating the rheological properties of raw and beneficiated Nigerian clays to ascertain their worth for use as drilling mud in oil and gas well drilling. This will save foreign earnings used in the importation of bentonite by the oil and gas development companies, create employment opportunity and open a new frontier for solid mineral development. Five clay samples from Pindiga Formation in Benue Trough, northeastern Nigeria were collected and subjected to elemental, rheological and other physical properties tests and analysis, while another portion of same samples were beneficiated using sodium carbonate, gum Arabic and poly-anionic cellulose for rheological enhancement then subjected to same cycle of tests and analysis above. Results obtained indicates that wet beneficiation as adopted in this study has proved to be more effective in Ca and Na ionic exchange. The rheological and other physical properties of the clays attained the standard that is required for use in oil and gas well drilling after addition of 12% sodium carbonate and 1.5 g poly-anionic cellulose. It was also discovered that when the formulation was allow to age (stay for 24 h, it attained optimum rheological requirement with 12% sodium carbonate and just 0.8 g poly-anionic cellulose. The clays studies do not require addition of weighing additive such as barite because of their high iron content which made their density attain the require standard even without additives. Keywords: Bentonitic clay, Beneficiation, Nigeria, Pindiga, Rheology, Mineralogy

  5. Generation of Anaphylatoxins by Human β-Tryptase from C3, C4, and C51

    Science.gov (United States)

    Fukuoka, Yoshihiro; Xia, Han-Zhang; Sanchez-Muñoz, Laura B.; Dellinger, Anthony L.; Escribano, Luis; Schwartz, Lawrence B.

    2009-01-01

    Both mast cells and complement participate in innate and acquired immunity. The current study examines whether β-tryptase, the major protease of human mast cells, can directly generate bioactive complement anaphylatoxins. Important variables included pH, monomeric vs tetrameric forms of β-tryptase, and the β-tryptase-activating polyanion. The B12 mAb was used to stabilize β-tryptase in its monomeric form. C3a and C4a were best generated from C3 and C4, respectively, by monomeric β-tryptase in the presence of low molecular weight dextran sulfate or heparin at acidic pH. High molecular weight polyanions increased degradation of these anaphylatoxins. C5a was optimally generated from C5 at acidic pH by β-tryptase monomers in the presence of high molecular weight dextran sulfate and heparin polyanions, but also was produced by β-tryptase tetramers under these conditions. Mass spectrometry verified that the molecular mass of each anaphylatoxin was correct. Both β-tryptase-generated C5a and C3a (but not C4a) were potent activators of human skin mast cells. These complement anaphylatoxins also could be generated by β-tryptase in releasates of activated skin mast cells. Of further biologic interest, β-tryptase also generated C3a from C3 in human plasma at acidic pH. These results suggest β-tryptase might generate complement anaphylatoxins in vivo at sites of inflammation, such as the airway of active asthma patients where the pH is acidic and where elevated levels of β-tryptase and complement anaphylatoxins are detected. PMID:18424754

  6. Insoluble (1 → 3), (1 → 4)-β-Dglucan is a component of cell walls in brown algae (Phaeophyceae) and is masked by alginates in tissues

    DEFF Research Database (Denmark)

    Salmeán, Armando A.; Duffieux, Delphine; Harholt, Jesper

    2017-01-01

    -rich cell-wall. Brown algal cell walls are composed predominantly of the polyanionic polysaccharides alginates and fucose-containing sulfated polysaccharides. These polymers are prevalent over neutral and crystalline components, which are believed to be mostly, if not exclusively, cellulose. In an attempt...... to better understand brown algal cell walls, we performed an extensive glycan array analysis of a wide range of brown algal species. Here we provide the first demonstration that mixed-linkage (1 → 3), (1 → 4)-β-d-glucan (MLG) is common in brown algal cell walls. Ultra-Performance Liquid Chromatography...

  7. Removal of radioactive cesium from surface soils solidified using polyion complex. Rapid communication for decontamination test at Iitate-mura in Fukushima Prefecture

    International Nuclear Information System (INIS)

    Naganawa, Hirochika; Yanase, Nobuyuki; Mitamura, Hisayoshi; Nagano, Tetsushi; Yoshida, Zenko; Kumazawa, Noriyuki; Saitoh, Hiroshi; Kashima, Kaoru; Fukuda, Tatsuya; Tanaka, Shun-ichi

    2011-01-01

    We tried the decontamination of surface soils for three types of agricultural land at Nagadoro district of Iitate-mura (village) in Fukushima Prefecture, which is highly contaminated by deposits of radionuclides from the plume released from the Fukushima Daiichi nuclear power plant. The decontamination method consisted of the peeling of surface soils solidified using a polyion complex, which was formed from a salt solution of polycations and polyanions. Two types of polyion complex solution were applied to an upland field in a plastic greenhouse, a pasture, and a paddy field. The decontamination efficiency of the surface soils reached 90%, and dust release was effectively suppressed during the removal of surface soils. (author)

  8. The Medicinal Chemistry of Therapeutic Oligonucleotides.

    Science.gov (United States)

    Wan, W Brad; Seth, Punit P

    2016-11-10

    Oligonucleotide-based therapeutics have made rapid progress in the clinic for treatment of a variety of disease indications. Unmodified oligonucleotides are polyanionic macromolecules with poor drug-like properties. Over the past two decades, medicinal chemists have identified a number of chemical modification and conjugation strategies which can improve the nuclease stability, RNA-binding affinity, and pharmacokinetic properties of oligonucleotides for therapeutic applications. In this perspective, we present a summary of the most commonly used nucleobase, sugar and backbone modification, and conjugation strategies used in oligonucleotide medicinal chemistry.

  9. Active site - a site of binding of affinity inhibitors in baker's yeast inorganic pyrophosphatase

    International Nuclear Information System (INIS)

    Svyato, I.E.; Sklyankina, V.A.; Avaeva, S.M.

    1986-01-01

    The interaction of the enzyme-substrate complex with methyl phosphate, O-phosphoethanolamine, O-phosphopropanolamine, N-acetylphosphoserine, and phosphoglyolic acid, as well as pyrophosphatase, modified by monoesters of phosphoric acid, with pyrophosphate and tripolyphosphate, was investigated. It was shown that the enzyme containing the substrate in the active site does not react with monophosphates, but modified pyrophosphatase entirely retains the ability to bind polyanions to the regulatory site. It is concluded that the inactivation of baker's yeast inorganic pyrophosphatase by monoesters of phosphoric acid, which are affinity inhibitors of it, is the result of modification of the active site of the enzyme

  10. Human DMBT1-Derived Cell-Penetrating Peptides for Intracellular siRNA Delivery

    DEFF Research Database (Denmark)

    Tuttolomondo, Martina; Casella, Cinzia; Hansen, Pernille Lund

    2017-01-01

    tumor 1) is a pattern recognition molecule that interacts with polyanions and recognizes and aggregates bacteria. Taking advantage of these properties, we investigated whether specific synthetic DMBT1-derived peptides could be used to formulate nanoparticles for siRNA administration. Using......-potential, circular dichroism, dynamic light scattering, and transmission electron microscopy revealed negatively charged nanoparticles with an average diameter of 10-800 nm, depending on the reaction conditions, and a spherical or rice-shaped morphology, depending on the peptide and β-helix conformation. We...

  11. Ionochromic 4,4 '-azobispyridinium salt-incorporated polymer: synthesis and optical properties

    Science.gov (United States)

    Lee, Taek Seung; Ahn, Heungki; Lee, Jin Kyun; Park, Won Ho

    2003-01-01

    Azobispyridinium-bearing polyelectrolyte linked with flexible alkyl chain was synthesized and characterized. The polymer showed absorption changes upon addition of hydroxide anion with an isobestic point in UV-visible spectrum. It is presumed that conformational change of the azo group in the main chain is responsible for the point. Transduction of physical information (hydroxide concentration) into an optical signal from azo group was related to the ionochromic effect. Electrostatic self-assembled multilayer of the polymer with appropriate polyanion was carried out via layer-by-layer deposition.

  12. NASICON Open Framework Structured Transition Metal Oxides for Lithium Batteries

    OpenAIRE

    Begam, K.M.; Michael, M.S.; Prabaharan, S.R.S.

    2010-01-01

    We identified a group of NASICON open framework structured polyanion materials and examined the materials for rechargeable lithium battery application. We found that the open framework structure of these materials facilitated easy insertion/extraction of lithium into/from their structure. We synthesized the materials in lithium-rich [Li2M2(MoO4)3] and lithium-free [LixM2(MoO4)3] (M= Ni, Co) phases, for the first time, by means of a low temperature soft-combustion technique. The soft-combustio...

  13. Impact of nutrient composition on a degradative biofilm community

    DEFF Research Database (Denmark)

    Møller, Søren; Korber, Darren R.; Wolfaardt, Gideon M.

    1997-01-01

    (Trypticase soy broth), the biofilms underwent an architectural change which included the loss of mound structures and the formation of a more homogeneous biofilm. Neutrally charged fluorescent dextrans, which upon hydration become cationic, were observed to bind to mounds, as well as to the basal cell layer......, in 14-day biofilms. In contrast, polyanionic dextrans bound only to the basal cell layer, indicating that this material incorporated sites with both positive and negative charge. The results from this study indicate that nutrient composition has a significant impact on both the architecture...

  14. Structure of ordered polyelectrolyte films from atomic-force microscopy and X-ray reflectivity data

    International Nuclear Information System (INIS)

    Belyaev, V.V.; Tolstikhina, A.L.; Stepina, N.D.; Kayushina, R.L.

    1998-01-01

    The possible application of atomic-force microscopy and X-ray reflectometry methods to structural studies of polyelectrolyte films obtained due to alternating adsorption of oppositely charged polyanion [sodium polysterenesulfonate (PSS)] and polycation [poly(allylamine) hydrochloride (PAA)] layers on solid substrates has been considered. The atomic-force microscopy study has revealed the characteristic features of the surface topography of samples consisting of different numbers of polyelectrolyte layers deposited from solutions characterized by different ionic strength values. It is shown that the shape of the reflectivity curves obtained from thin polyelectrolyte films depends on their surface structure

  15. A promising cellulose-based polyzwitterion with pH-sensitive charges

    Directory of Open Access Journals (Sweden)

    Thomas Elschner

    2014-07-01

    Full Text Available A novel polyzwitterion possessing weak ionic groups could be efficiently synthesized from cellulose phenyl carbonate. Polyanion, polycation, and polyzwitterion are accessible by orthogonal removal of protecting groups. The molecular structure was proofed by FTIR- and NMR spectroscopy. Characteristic properties of the cellulose derivatives, e.g., acid dissociation constants, isoelectric point and complexation, were investigated by potentiometric titration (pH, nephelometry, rheology and dynamic light-scattering. The formation of pH-responsive interpolyelectrolyte complexes applying polydiallyldimethylammonium chloride was preliminary studied.

  16. The blue complexes of U in aqueous solutions

    International Nuclear Information System (INIS)

    Musikas, C.

    1976-01-01

    Mixed-valence uranium complexes were synthesized. Hydrolysis of hexavalent U leads to anionic species soluble in aqueous solutions when the UO 2 ++ ions are neutralized by tetraalkylammonium hydroxides. These complexes are polynuclear and the size and interatomic distances found for the polyanions are those of macromolecules. By hydrazine of these complexes, solutions were obtained and their absorption spectra studied. The spectra of U(VI) and U(V) ions are observed, together with new bands attributable to a charge transfer. It may be concluded that the blue complexes of uranium are type II composite-valence complexes for which the delocalization coefficient α can be calculated [fr

  17. Preparation and characterization of depolymerised chitosan films and crosslinked with sodium tripolyphosphate

    International Nuclear Information System (INIS)

    Salazar, Max Carlos; Valderrama Negron, Ana

    2013-01-01

    This work has studied the preparation and characterization of chitosan films (CS) crosslinked with sodium tripolyphosphate (TPP), prepared by the solvent evaporation method. Initially we studied the depolymerization of chitosan with sodium nitrite to get different polymer molecular weights in the used polymer. For example, we obtained chitosans of 554.22kDa and 133.37kDa of molecular weight. Afterward, prepared and characterized chitosans films crosslinked with TPP, evidently the hydrogen bridge interaction with the polyanion through IR, SEM, TG; also was performed swelling studies, with the objective of identified the type of kinetic model in which enable explain said phenomenon in these films. (author)

  18. Les diatomées et les indices diatomiques dans les réseaux de mesure de la qualité des cours d'eau français : historique et avenir

    Directory of Open Access Journals (Sweden)

    PRYGIEL J.

    1996-04-01

    Full Text Available L'utilisation des diatomées et des indices diatomiques dans les réseaux français de mesure de la qualité des eaux a débuté en 1970, sur la Seine. Un regain d'intérêt s'est manifesté à partir des années 1990, avec des applications sur les bassins Rhône-Méditerranée-Corse, Artois- Picardie, Rhin-Meuse et Adour-Garonne. En 1994, les Agences se sont associées avec le CEMAGREF pour mettre au point un indice diatomique applicable en routine sur l'ensemble du territoire français, et pour promouvoir et faciliter son utilisation en réseau de surveillance. Cet indice diatomique doit rejoindre l'Indice Biologique Global Normalisé au sein du volet biologique du futur système d'évaluation de la qualité des cours d'eau, actuellement en cours de réalisation. Les développements doivent désormais porter sur la consolidation de cet indice au niveau français, ainsi que sur des tests dans plusieurs pays européens.

  19. Prostate cancer treatment in Europe at the end of 1990s

    International Nuclear Information System (INIS)

    Gatta, Gemma; Zigon, Giulia; Buemi, Antoine

    2009-01-01

    Background. There is wide variation in prostate cancer incidence and survival across Europe. In many countries incidence is rising sharply in relation to the introduction of prostate-specific antigen assay, and there is concern that patients may not be treated appropriately. We therefore aimed to characterize treatment for prostate cancer across Europe. Methods. We performed a high resolution population-based study, collecting information on the treatment of 3 486 prostate cancer cases diagnosed in 1995-1999 in 11 cancer registries from six European countries. Results. Overall, about one in three patients received radical treatment (prostatectomy 23% or radiotherapy 14%); about 60% of younger patients ( 70% in Civilised, Haut-Rh in, Tarn and Eindhoven and <50% in Slovakia and Cracow. Overall 34% of patients with apparently low-risk disease received radical treatment, varying from 17% and 22% in Bas-Rhin and Granada, to 52% and 56% in Calvados and Eindhoven. Conclusions. Our data indicate wide variation in the treatment for prostate cancer even among patients with apparently similar disease, and further suggest a non-negligible proportion may be receiving inappropriate radical treatment for apparently low-risk disease. Current guidelines indicate active surveillance should become the main means of managing low-risk disease

  20. Towards the onset of fruit tree growing north of the Alps: ancient DNA from waterlogged apple (Malus sp.) seed fragments.

    Science.gov (United States)

    Schlumbaum, Angela; van Glabeke, Sabine; Roldan-Ruiz, Isabel

    2012-01-20

    Wild apples (Malus sp.) have been a major food source in the northern Alpine region since prehistory and their use is well understood. The onset of deliberate fruit tree growing in the area is, however, less clear. It is generally assumed that horticulture was practised in Roman times, but it might be even earlier. In the archaeological record seed testa and pericarp remains are particularly frequent at sites with waterlogged preservation such as lakeshore settlements or wells, pits and ditches, but the distinction between wild and domestic plants is not morphologically possible. With waterlogged remains being one main source of information about past fruit cultivation, we have tested the feasibility of analysing ancient DNA from waterlogged preserved bulk samples of testa fragments. We studied apple seeds from three Neolithic and three Roman sites with waterlogged preservation in the Alpine foreland. Chloroplast markers failed in all samples, but nuclear ITS1 (internal transcribed spacer region 1) of the ribosomal DNA was successfully typed in two Roman samples from the site Oedenburg/Biesheim-Kunheim (Haut-Rhin, F). The retrieved ITS1 sequences are identical to each other and are shared with wild Malus sylvestris and Malus sieversii, and with domestic apple cultivars, supporting the potential of using waterlogged remains for identifying the genetic status of apple diachronically. Copyright © 2011 Elsevier GmbH. All rights reserved.

  1. Nuclear safety and radiation protection report of the Fessenheim nuclear facilities - 2011

    International Nuclear Information System (INIS)

    2012-01-01

    This safety report was established under the article 21 of the French law no. 2006-686 of June 13, 2006 relative to nuclear safety and information transparency. It presents, first, the facilities of the Fessenheim nuclear power plant (INB 75, Haut-Rhin, 68 (FR)). Then, the nuclear safety and radiation protection measures taken regarding the facilities are reviewed: nuclear safety definition, radiation protection of intervening parties, safety and radiation protection improvement paths, crisis management, external and internal controls, technical situation of facilities, administrative procedures in progress. The incidents and accidents which occurred in 2011, are reported as well as the radioactive and non-radioactive (chemical, thermal) effluents discharge in the environment. Finally, The radioactive materials and wastes generated by the facilities are presented and sorted by type of waste, quantities and type of conditioning. Other environmental impacts (noise) are presented with their mitigation measures. Actions in favour of transparency and public information are presented as well. The document concludes with a glossary and a list of recommendations from the Committees for health, safety and working conditions. (J.S.)

  2. A Study on the Frequency of Fungal Rhinosinusitis and to Determine the Sensitivity of the Isolates to Antifungal Drugs in Shiraz, Iran 2012-2013

    Directory of Open Access Journals (Sweden)

    Parisa Badiei

    2015-06-01

    Full Text Available Abstract Background: Fungal spores are present in large amounts in the nature which may cause diseases in the susceptible individuals. Fungal rhinosinusitis has been increased during recent decades. This study aims to investigate fungal rhinosinusitis in the patients with chronic needing endoscopic sinus surgery aims and to determine the sensitivity of the isolates to rhin sinusitis antifungal agents. Materials and Methods: In cross sectional study, specimens were obtained in sterile plates containing normal saline. from the suspected cases of chronic rhinosinusitis who had undergone endoscopic sinus surgery. Microscopic experiments and Cultures were done in Sabouraud Dextrose Agar medium. Minimum inhibitory concentration (MIC of the growth of fungi for seven antifungal agents against the isolates was determined using E-Test. Results: In total, specimens from 102 immunocompetent patients were examined. Nine positive specimens were presented, consisting of 3 for Aspergillus fumigatus, 3 for Penicillium, 2 for Aspergillus flavus and 1 for Alternaria. The mean age of the patients was 38 years, with 59 males and 43 females. The isolates were most sensitive to the voriconazole and amphotericin B. Conclusion: Since the prevalence of fungal rhinosinusitis is low, unfortunately, the clinicians are not attentive enough to the condition, and they initiate antifungal therapy if the patients are not responsive to antibiotics. Early diagnosis and suitable treatment can help more efficient management of patients.

  3. Uraniferous schists of the Alsacian side of Vosges mountains; Les schistes uraniferes du versant Alsacien des Vosges Moyennes

    Energy Technology Data Exchange (ETDEWEB)

    Grimbert, A; Carlier, A [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1957-07-01

    Since the discover of uraniferous schists in 1951 in the Ribeauville region (Haut-Rhin), the atomic energy commission has been interested in low content uranium deposits. It originated in France a new interest in uranium sedimentary deposit which were, until now, of a less interest than deposits in crystalline vein-stone. A general description of the oriental versant of Vosges mountains is given and a petrographical and tectonic study is described as well as the mineralization and radioactivity of the region. It studied in particular the uranium deposits near the Schaentzel summit. An historic of the local research is given as well as a study of the borings. A description of the different rock formations, which have been found on the site, is given: sandstone, schists, arkoses, granites. A comparison of the Schaentzel uraniferous schists with other known uraniferous schists is made. finally, interpretations of the study and origin of the uraniferous mineralization in Schaentzel sedimentary deposits are discussed. (M.P.)

  4. Nuclear safety and radiation protection report of the Fessenheim nuclear facilities - 2010

    International Nuclear Information System (INIS)

    2011-06-01

    This safety report was established under the article 21 of the French law no. 2006-686 of June 13, 2006 relative to nuclear safety and information transparency. It presents, first, the facilities of the Fessenheim nuclear power plant (INB 75, Haut-Rhin, 68 (FR)). Then, the nuclear safety and radiation protection measures taken regarding the facilities are reviewed: nuclear safety definition, radiation protection of intervening parties, safety and radiation protection improvement paths, crisis management, external and internal controls, technical situation of facilities, administrative procedures in progress. The incidents and accidents which occurred in 2010, are reported as well as the radioactive and non-radioactive (chemical, thermal) effluents discharge in the environment. Finally, The radioactive materials and wastes generated by the facilities are presented and sorted by type of waste, quantities and type of conditioning. Other environmental impacts (noise) are presented with their mitigation measures. Actions in favour of transparency and public information are presented as well. The document concludes with a glossary and a list of recommendations from the Committees for health, safety and working conditions. (J.S.)

  5. Geothermal energy

    International Nuclear Information System (INIS)

    Le Du, H.; Bouchot, V.; Lopez, S.; Bialkowski, A.; Colnot, A.; Rigollet, C.; Sanjuan, B.; Millot, R.; Brach, M.; Asmundsson, R.; Giroud, N.

    2010-01-01

    Geothermal energy has shown a revival for several years and should strongly develop in a near future. Its potentiality is virtually unexhaustible. Its uses are multiple and various: individual and collective space heating, heat networks, power generation, heat storage, heat exchanges etc.. Re-launched by the demand of renewable energy sources, geothermal energy has become credible thanks to the scientific works published recently which have demonstrated its economical and technical relevance. Its image to the public is changing as well. However, lot of work remains to do to make geothermal energy a real industry in France. Several brakes have to be removed rapidly which concern the noise pollution of geothermal facilities, the risk of bad results of drillings, the electricity costs etc. This dossier gives an overview of today's main research paths in the domain of geothermal energy: 1 - geothermal energy in France: historical development, surface and deep resources, ambitions of the French national energy plan (pluri-annual investment plan for heat generation, incentives, regional 'climate-air-energy' schemes), specific regulations; 2 - geothermal energy at the city scale - sedimentary basins: Ile-de-France 40 years of Dogger reservoir exploitation, potentialities of clastic reservoirs - the Chaunoy sandstones example; 3 - geothermal power generation: conventional reservoirs - the Bouillante model (Guadeloupe, French Indies); the Soultz-sous-Forets pilot plant (Bas-Rhin, France); the supercritical reservoirs - the Krafla geothermal area (Iceland). (J.S.)

  6. Two inorganic-organic hybrid materials based on polyoxometalate anions and methylene blue: Preparations, crystal structures and properties

    International Nuclear Information System (INIS)

    Nie Shanshan; Zhang Yaobin; Liu Bin; Li Zuoxi; Hu Huaiming; Xue Ganglin; Fu Feng; Wang Jiwu

    2010-01-01

    Two novel inorganic-organic hybrid materials based on an organic dye cation methylene blue (MB) and Lindqvist-type POM polyanions, [C 22 H 18 N 3 S] 2 Mo 6 O 19 2DMF (1) and [C 22 H 18 N 3 S] 2 W 6 O 19 2DMF (2) were synthesized under ambient conditions and characterized by CV, IR spectroscopy, solid diffuse reflectance spectrum, UV-vis spectra in DMF solution, luminescent spectrum and single crystal X-ray diffraction. Crystallographic data reveal that compounds 1 and 2 are isostructural and both crystallize in the triclinic space group P1-bar . Their crystal structures present that the layers of organic molecules and inorganic anions array alternatively, and there exist strong π...π stacking interactions between dimeric MB cations and near distance interactions among organic dye cations, Lindqvist-type POM polyanions and DMF molecules. The solid diffuse reflectance spectra and UV-vis spectra in DMF solution appear new absorption bands ascribed to the charge-transfer transition between the cationic MB donor and the POM acceptors. Studies of the photoluminescent properties show that the formation of 1 and 2 lead to the fluorescence quenching of starting materials. -- Graphical abstract: Their crystal structures present that the layers of organic molecules and inorganic anions array alternatively, and there exist strong π...π stacking interactions between dimeric MB cations. Display Omitted

  7. Ab initio investigations of the electronic structures and chemical bonding in LiCo{sub 6}P{sub 4} and Li{sub 2}Co{sub 12}P{sub 7}

    Energy Technology Data Exchange (ETDEWEB)

    Matar, Samir F. [CNRS, ICMCB, UPR 9048, F‐33600 Pessac (France); Université de Bordeaux, ICMCB, UPR 9048, F‐33600 Pessac (France); Al-Alam, Adel; Ouaini, Naïm [Université Saint-Esprit de Kaslik (USEK), Groupe OCM (Optimization et Caractérisation des Matériaux), CSR-USEK, CNRS-L, Jounieh (Lebanon); Pöttgen, Rainer, E-mail: pottgen@uni-muenster.de [Institut für Anorganische und Analytische Chemie, Universität Münster, Corrensstraße 30, D-48149 Münster (Germany)

    2013-06-15

    The electronic structures of the metal-rich phosphides LiCo{sub 6}P{sub 4} and Li{sub 2}Co{sub 12}P{sub 7} were studied by DFT calculations. Both phosphides consist of three-dimensional [Co{sub 6}P{sub 4}] and [Co{sub 12}P{sub 7}] polyanionic networks which leave hexagonal channels for the lithium atoms. COOP data show strong Co–P and Co–Co bonding within the polyanions. The lithium atoms have trigonal prismatic phosphorus coordination. Total energy calculations indicate stability upon de-lithiation towards the Co{sub 6}P{sub 4} and Co{sub 12}P{sub 7} substructures - Graphical abstract: The cobalt–phosphorus networks in LiCo{sub 6}P{sub 4} and Li{sub 2}Co{sub 12}P{sub 7}. - Highlights: • Chemical bonding resolved in the metal-rich phosphides LiCo{sub 6}P{sub 4} and Li{sub 2}Co{sub 12}P{sub 7}. • Strong covalent Co–P bonding character in the [Co{sub 6}P{sub 4}] and [Co{sub 12}P{sub 7}] substructures. • Total energy calculations indicate stability of the de-lithiated substructures.

  8. The gold-rich indide Sr{sub 5}Au{sub 13.5}In{sub 8.5}

    Energy Technology Data Exchange (ETDEWEB)

    Muts, Ihor [Ivan Franko National Univ. of Lviv (Ukraine). Inorganic Chemistry Dept.; Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie; Rodewald, Ute C.; Poettgen, Rainer [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie; Zaremba, Vasyl' I. [Ivan Franko National Univ. of Lviv (Ukraine). Inorganic Chemistry Dept.

    2011-11-15

    The orthorhombic indide Sr{sub 5}Au{sub 13.5}In{sub 8.5} was obtained during phase-analytical studies of the Sr-Au-In system. This new indide is formed upon melting of the elements in a sealed tantalum tube. Sr{sub 5}Au{sub 13.5}In{sub 8.5} was characterized on the basis of powder and single-crystal X-ray diffraction: Pmmn, a = 476.37(9), b = 2927.5(9), c = 894.9(2) pm, wR2 = 0.056, 2355 F{sup 2} values, 87 variables. The structure is of a new type. The gold and indium atoms build up a complex three-dimensional [Au{sub 13.5}In{sub 8.5}] polyanionic network in which the strontium atoms fill channels which extend in the a direction. One site within the polyanion shows Au/In mixing. The Sr{sub 5}Au{sub 13.5}In{sub 8.5} structure is composed of SrAu{sub 3}In{sub 3-} and SrAu-related slabs. (orig.)

  9. Studies on uranium ore processing

    International Nuclear Information System (INIS)

    Suh, I.S.; Chun, J.K.; Park, S.W.; Choi, S.J.; Lee, C.H.; Chung, M.K.; Lim, J.K.

    1983-01-01

    For the exploitation of domestic uranium ore deposit, comprehensive studies on uranium ore processing of the Geum-San pit ore are carried out. Physical and chemical characteristics of the Geum-San ore are similar to those of Goe-San ore and the physical beneficiation could not be applicable. Optimum operating conditions such as uranium leaching, solid-liquid separation, solvent extraction and precipitation of yellow cake are found out and the results are confirmed by the continous operation of the micro-plant with the capacity of 50Kg, ore/day. In order to improve the process of ore milling pilot plant installed recently, the feasibility of raffinate-recycle and the precipitation methods of yellow cake are intensively examined. It was suggested that the raffinate-recycle in the leaching of filtering stage could be reduced the environmental contamination and the peroxide precipitation technique was applicable to improve the purity of yellow cake. The mechanism and conditions the third phase formation are thoroughly studied and confirmed by chemical analysis of the third phase actually formed during the operation of pilot plant. The major constituents of the third phase are polyanions such as PMosub(12)Osub(40)sup(3-) or SiMosub(12)Osub(40)sup(4-). And the formation of these polyanions could be reduced by the control of redox potential and the addition of modifier. (Author)

  10. Microscopic Characterization of Individual Submicron Bubbles during the Layer-by-Layer Deposition: Towards Creating Smart Agents

    Science.gov (United States)

    Kato, Riku; Frusawa, Hiroshi

    2015-07-01

    We investigated the individual properties of various polyion-coated bubbles with a mean diameter ranging from 300 to 500 nm. Dark field microscopy allows one to track the individual particles of the submicron bubbles (SBs) encapsulated by the layer-by-layer (LbL) deposition of cationic and anionic polyelectrolytes (PEs). Our focus is on the two-step charge reversals of PE-SB complexes: the first is a reversal from negatively charged bare SBs with no PEs added to positive SBs encapsulated by polycations (monolayer deposition), and the second is overcharging into negatively charged PE-SB complexes due to the subsequent addition of polyanions (double-layer deposition). The details of these phenomena have been clarified through the analysis of a number of trajectories of various PE-SB complexes that experience either Brownian motion or electrophoresis. The contrasted results obtained from the analysis were as follows: an amount in excess of the stoichiometric ratio of the cationic polymers was required for the first charge-reversal, whereas the stoichiometric addition of the polyanions lead to the electrical neutralization of the PE-SB complex particles. The recovery of the stoichiometry in the double-layer deposition paves the way for fabricating multi-layered SBs encapsulated solely with anionic and cationic PEs, which provides a simple protocol to create smart agents for either drug delivery or ultrasound contrast imaging.

  11. Effect of cationic grafted copolymer structure on the encapsulation of bovine serum albumin

    International Nuclear Information System (INIS)

    Flynn, Nicholas; Topal, Ç. Özge; Hikkaduwa Koralege, Rangika S.; Hartson, Steve; Ranjan, Ashish; Liu, Jing; Pope, Carey; Ramsey, Joshua D.

    2016-01-01

    The aim of the present study was to evaluate a library of poly-L-lysine (PLL)-graft (g)-polyethylene glycol (PEG) copolymers for the ability to encapsulate effectively a model protein, bovine serum albumin (BSA), and to characterize the stability and protein function of the resulting nanoparticle. A library of nine grafted copolymers was produced by varying PLL molecular weight and PEG grafting ratio. Electrostatic self-assembly of the protein and the grafted copolymer drove encapsulation. The formation of protein/polymer nanoparticles with a core/shell structure was confirmed using PAGE, dynamic light scattering, and electron microscopy. Encapsulation of the BSA into nanoparticles was strongly dependent on the copolymer-to-protein mass ratio, PEG grafting ratio, and PLL molecular weight. A copolymer-to-protein mass ratio of 7:1 and higher was generally required for high levels of encapsulation, and under these conditions, no loss of protein activity was observed. Copolymer characteristics also influenced nanoparticle resistance to polyanions and protease degradation. The results indicate that a copolymer of 15–30 kDa PLL, with a PEG grafting ratio of 10:1, is most promising for protein delivery. - Highlights: • A 4–70 kDa range of PLL-g-PEG copolymers was able to encapsulate BSA into NPs. • Encapsulation of BSA by PLL-g-PEG not only retained but increased esterolytic activity. • NPs were stable against protease degradation and polyanion dissociation.

  12. Reaction enthalpy from the binding of multivalent cations to anionic polyelectrolytes in dilute solutions

    Science.gov (United States)

    Hansch, Markus; Kaub, Hans Peter; Deck, Sascha; Carl, Nico; Huber, Klaus

    2018-03-01

    Dilute solutions of sodium poly(styrene sulfonate) (NaPSS) in the presence of Al3+, Ca2+, and Ba2+ were analysed by means of isothermal titration calorimetry (ITC) in order to investigate the heat effect of bond formation between those cations and the anionic SO3- residues of NaPSS. The selection of the cations was guided by the solution behavior of the corresponding PSS salts from a preceding study [M. Hansch et al., J. Chem. Phys. 148(1), 014901 (2018)], where bonds between Ba2+ and anionic PSS showed an increasing solubility with decreasing temperature and Al3+ exhibited the inverse trend. Unlike to Al3+ and Ba2+, Ca2+ is expected to behave as a purely electrostatically interacting bivalent cation and was thus included in the present study. Results from ITC satisfactorily succeeded to explain the temperature-dependent solution behavior of the salts with Al3+ and Ba2+ and confirmed the non-specific behavior of Ca2+. Additional ITC experiments with salts of Ca2+ and Ba2+ and sodium poly(acrylate) complemented the results on PSS by data from a chemically different polyanion. Availability of these joint sets of polyanion-cation combinations not only offers the chance to identify common features and subtle differences in the solution behavior of polyelectrolytes in the presence of multi-valent cations but also points to a new class of responsive materials.

  13. Electrometric studies on the isopolyanions of Vanadium (V)

    Energy Technology Data Exchange (ETDEWEB)

    Prasad, S [Paraiba Univ., Joao Pessoa (Brazil). Dept. de Engenharia Quimica

    1981-09-01

    The stoichiometry of various polyanions formed during the reaction between acids (H/sub 2/SO/sub 4/, HClO/sub 4/) and alkali ortho-vanadate (3Na/sub 2/O.V/sub 2/O/sub 5/) has been investigated by means of electrometric techniques involving pH, E.M.F. and conductometric titrations as well as by job's method of continuous variation. The well defined breaks and inflections in titration curves and maxima from continuous variation study provide cogent evidence for the existence of aggregated polyanions, pyro-V/sub 2/O/sub 7//sup 4 -/, meta-VO/sub 3//sup 1 -/ and poly-V/sub 10/O/sub 27//sup 4 -/ vanadates corresponding to the ratios of VO/sub 4//sup 3 -/:H/sup +/ as 1:1, 1:2 and 1:2.6 in the pH ranges (9.3-9.9), (6.6-7.2) and (3.6-4.2), respectively.

  14. In Situ Tracking Kinetic Pathways of Li+/Na+ Substitution during Ion-Exchange Synthesis of LixNa1.5-xVOPO4F0.5.

    Science.gov (United States)

    Park, Young-Uk; Bai, Jianming; Wang, Liping; Yoon, Gabin; Zhang, Wei; Kim, Hyungsub; Lee, Seongsu; Kim, Sung-Wook; Looney, J Patrick; Kang, Kisuk; Wang, Feng

    2017-09-13

    Ion exchange is a ubiquitous phenomenon central to wide industrial applications, ranging from traditional (bio)chemical separation to the emerging chimie douce synthesis of materials with metastable structure for batteries and other energy applications. The exchange process is complex, involving substitution and transport of different ions under non-equilibrium conditions, and thus difficult to probe, leaving a gap in mechanistic understanding of kinetic exchange pathways toward final products. Herein, we report in situ tracking kinetic pathways of Li + /Na + substitution during solvothermal ion-exchange synthesis of Li x Na 1.5-x VOPO 4 F 0.5 (0 ≤ x ≤ 1.5), a promising multi-Li polyanionic cathode for batteries. The real-time observation, corroborated by first-principles calculations, reveals a selective replacement of Na + by Li + , leading to peculiar Na + /Li + /vacancy orderings in the intermediates. Contradicting the traditional belief of facile topotactic substitution via solid solution reaction, an abrupt two-phase transformation occurs and predominantly governs the kinetics of ion exchange and transport in the 1D polyanionic framework, consequently leading to significant difference of Li stoichiometry and electrochemical properties in the exchanged products. The findings may help to pave the way for rational design of ion exchange synthesis for making new materials.

  15. Microscopic Characterization of Individual Submicron Bubbles during the Layer-by-Layer Deposition: Towards Creating Smart Agents

    Directory of Open Access Journals (Sweden)

    Riku Kato

    2015-07-01

    Full Text Available We investigated the individual properties of various polyion-coated bubbles with a mean diameter ranging from 300 to 500 nm. Dark field microscopy allows one to track the individual particles of the submicron bubbles (SBs encapsulated by the layer-by-layer (LbL deposition of cationic and anionic polyelectrolytes (PEs. Our focus is on the two-step charge reversals of PE-SB complexes: the first is a reversal from negatively charged bare SBs with no PEs added to positive SBs encapsulated by polycations (monolayer deposition, and the second is overcharging into negatively charged PE-SB complexes due to the subsequent addition of polyanions (double-layer deposition. The details of these phenomena have been clarified through the analysis of a number of trajectories of various PE-SB complexes that experience either Brownian motion or electrophoresis. The contrasted results obtained from the analysis were as follows: an amount in excess of the stoichiometric ratio of the cationic polymers was required for the first charge-reversal, whereas the stoichiometric addition of the polyanions lead to the electrical neutralization of the PE-SB complex particles. The recovery of the stoichiometry in the double-layer deposition paves the way for fabricating multi-layered SBs encapsulated solely with anionic and cationic PEs, which provides a simple protocol to create smart agents for either drug delivery or ultrasound contrast imaging.

  16. Synthesis and Characterization of the Ternary Thiobismuthates A9Bi13S24 (A = K, Rb)

    KAUST Repository

    Davaasuren, Bambar

    2016-11-16

    Ternary alkali metal thiobismuthates ABiS (A = K, Rb) were synthesized by direct combination reactions at 650 °C. The compounds crystallize in the monoclinic space group C2/m (no. 12) with cell parameters a = 30.919(1) Å, b = 4.1008(2) Å, c = 20.9072(9) Å, β = 105.826(3)° for KBiS (1) and a = 31.823(6) Å, b = 4.1177(8) Å, c = 21.086(4) Å, β = 105.62(3)° for RbBiS (2). The crystal structure of 1 contains a 3D [KBiS] polyanionic framework, whereas 2 consists of 2D [RbBiS] polyanionic slabs stacked along [201]. Both 1 and 2 are semiconductors with a band gap of 1.4 and 1.3 eV, respectively, which is supported by an electronic structure calculation. 1 melts congruently at 580 °C, while 2 melts incongruently at 575 °C. 1 and 2 are airstable and insoluble in water and organic solvents.

  17. Intracrystalline site preference of hydrogen isotopes in borax

    International Nuclear Information System (INIS)

    Pradhananga, T.M.; Matsuo, S.

    1985-01-01

    The total hydrogen involved in borax synthesized at 25 0 C in aqueous solution is enriched in deuterium by 5.3% compared with the mother liquor. There is no change in the value of the D/H fractionation factor between the hydrogen in borax and those in the mother liquor with changes in the degree of supersaturation. The fractionation factor changes slightly with a change in the crystallization temperature of borax in the range from 5 to 25 0 C. The D/H ratio in the different sites of borax was estimated by a fractional dehydration technique. The results show that hydrogen atoms of the polyanionic group [B 4 O 5 (OH) 4 ] are much more enriched in deuterium than those of the cationic group [Na 2 x 8H 2 O]. The delta D values, referred to the mother liquor from which the borax was crystallized, for the cationic group (site A) and the polyanionic group (site B) are -35 +/- 3 and 167 +/- 13%, respectively based on the fractional dehydration results obtained at -21 0 C. At -21 0 C, isotopic exchange between different sites during dehydration is assumed not to occur. The mechanism for dehydration of borax is discussed. 48 references, 8 figures, 3 tables

  18. Fabrication and properties of light-emitting diodes based on self-assembled multilayers of poly(phenylene vinylene)

    Science.gov (United States)

    Fou, A. C.; Onitsuka, O.; Ferreira, M.; Rubner, M. F.; Hsieh, B. R.

    1996-05-01

    Light-emitting diodes have been fabricated from self-assembled multilayers of poly(p-phenylene vinylene) (PPV) and two different polyanions; polystyrene sulfonic acid (SPS) and polymethacrylic acid (PMA). The type of polyanion used to assemble the multilayer thin films was found to dramatically influence the behavior and performance of devices fabricated with indium tin oxide and aluminum electrodes. Light-emitting devices fabricated from PMA/PPV multilayers were found to exhibit luminance levels in the range of 20-60 cd/m2, a thickness dependent turn-on voltage and classical rectifying behavior with rectification ratios greater than 105. In sharp contrast, the devices based on SPS/PPV exhibited near symmetric current-voltage curves, thickness independent turn-on voltages and much lower luminance levels. The significant difference in device behavior observed between these two systems is primarily due to a doping effect induced either chemically or electrochemically by the sulfonic acid groups of SPS. It was also found that the performance of these devices depends on the type of layer that is in contact with the Al top electrode thereby making it possible to manipulate device efficiency at the molecular level.

  19. From cation to oxide: hydroxylation and condensation of aqueous complexes

    International Nuclear Information System (INIS)

    Jolivet, J.P.

    1997-01-01

    Hydroxylation, condensation and precipitation of metal cations in aqueous solution are briefly reviewed. Hydroxylation of aqueous complexes essentially depends on the format charge (oxidation state), the size and the pH of the medium. It is the step allowing the condensation reaction. Depending on the nature of complexes (aqua-hydroxo, oxo-hydroxo), the. mechanism of condensation is different, olation or ox-olation respectively. The first one leads to poly-cations or hydroxides more or less stable against dehydration. The second one leads to poly-anions or oxides. Oligomeric species (poly-cations, poly-anions) are form from charged monomer complexes while the formation of solid phases requires non-charged precursors. Because of their high lability, charged oligomers are never the precursors of solids phases. The main routes for the formation of solid phases from solution are studied with two important and representative elements, Al and Si. For Al 3+ ions, different methods (base addition in solution, thermo-hydrolysis, hydrothermal synthesis) are discussed in relation to the crystal structure of the solid phase obtained. For silicic species condensing by ox-olation, the role of acid or base catalysis on the morphology of gels is studied. The influence of complexing ligands on the processes and on the characteristics of solids (morphology of particles, basic salts and polymetallic oxides formation) is studied. (author)

  20. Electronic structure and chemical bonding in LaIrSi-type intermetallics

    Energy Technology Data Exchange (ETDEWEB)

    Matar, Samir F. [Bordeaux Univ., Pessac (France). CNRS; Poettgen, Rainer [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie; Nakhl, Michel [Univ. Libanaise, Fanar (Lebanon). Ecole Doctorale Sciences et Technologies

    2017-05-01

    The cubic LaIrSi type has 23 representatives in aluminides, gallides, silicides, germanides, phosphides, and arsenides, all with a valence electron count of 16 or 17. The striking structural motif is a three-dimensional network of the transition metal (T) and p element (X) atoms with TX{sub 3/3} respectively XT{sub 3/3} coordination. Alkaline earth or rare earth atoms fill cavities within the polyanionic [TX]{sup δ-} networks. The present work presents a detailed theoretical study of chemical bonding in LaIrSi-type representatives, exemplarily for CaPtSi, BaIrP, BaAuGa, LaIrSi, CeRhSi, and CeIrSi. DFT-GGA-based electronic structure calculations show weakly metallic compounds with itinerant small magnitude DOSs at E{sub F} except for CeRhSi whose large Ce DOS at E{sub F} leads to a finite magnetization on Ce (0.73 μ{sub B}) and induced small moments of opposite sign on Rh and Si in a ferromagnetic ground state. The chemical bonding analyses show dominant bonding within the [TX]{sup δ-} polyanionic networks. Charge transfer magnitudes were found in accordance with the course of the electronegativites of the chemical constituents.

  1. Modeling competitive substitution in a polyelectrolyte complex

    International Nuclear Information System (INIS)

    Peng, B.; Muthukumar, M.

    2015-01-01

    We have simulated the invasion of a polyelectrolyte complex made of a polycation chain and a polyanion chain, by another longer polyanion chain, using the coarse-grained united atom model for the chains and the Langevin dynamics methodology. Our simulations reveal many intricate details of the substitution reaction in terms of conformational changes of the chains and competition between the invading chain and the chain being displaced for the common complementary chain. We show that the invading chain is required to be sufficiently longer than the chain being displaced for effecting the substitution. Yet, having the invading chain to be longer than a certain threshold value does not reduce the substitution time much further. While most of the simulations were carried out in salt-free conditions, we show that presence of salt facilitates the substitution reaction and reduces the substitution time. Analysis of our data shows that the dominant driving force for the substitution process involving polyelectrolytes lies in the release of counterions during the substitution

  2. Effect of cationic grafted copolymer structure on the encapsulation of bovine serum albumin

    Energy Technology Data Exchange (ETDEWEB)

    Flynn, Nicholas [School of Chemical Engineering, Oklahoma State University, Stillwater, OK 74078 (United States); Topal, Ç. Özge [School of Mechanical and Aerospace Engineering, Oklahoma State University, Stillwater, OK 74078 (United States); Hikkaduwa Koralege, Rangika S. [School of Chemical Engineering, Oklahoma State University, Stillwater, OK 74078 (United States); Hartson, Steve [Department of Biochemistry and Molecular Biology, Oklahoma State University, Stillwater, OK 74078 (United States); Ranjan, Ashish; Liu, Jing; Pope, Carey [Department of Physiological Sciences, Oklahoma State University, Stillwater, OK 74078 (United States); Ramsey, Joshua D., E-mail: josh.ramsey@okstate.edu [School of Chemical Engineering, Oklahoma State University, Stillwater, OK 74078 (United States)

    2016-05-01

    The aim of the present study was to evaluate a library of poly-L-lysine (PLL)-graft (g)-polyethylene glycol (PEG) copolymers for the ability to encapsulate effectively a model protein, bovine serum albumin (BSA), and to characterize the stability and protein function of the resulting nanoparticle. A library of nine grafted copolymers was produced by varying PLL molecular weight and PEG grafting ratio. Electrostatic self-assembly of the protein and the grafted copolymer drove encapsulation. The formation of protein/polymer nanoparticles with a core/shell structure was confirmed using PAGE, dynamic light scattering, and electron microscopy. Encapsulation of the BSA into nanoparticles was strongly dependent on the copolymer-to-protein mass ratio, PEG grafting ratio, and PLL molecular weight. A copolymer-to-protein mass ratio of 7:1 and higher was generally required for high levels of encapsulation, and under these conditions, no loss of protein activity was observed. Copolymer characteristics also influenced nanoparticle resistance to polyanions and protease degradation. The results indicate that a copolymer of 15–30 kDa PLL, with a PEG grafting ratio of 10:1, is most promising for protein delivery. - Highlights: • A 4–70 kDa range of PLL-g-PEG copolymers was able to encapsulate BSA into NPs. • Encapsulation of BSA by PLL-g-PEG not only retained but increased esterolytic activity. • NPs were stable against protease degradation and polyanion dissociation.

  3. Spectroscopic studies of sulfite-based polyoxometalates at high temperature and high pressure

    International Nuclear Information System (INIS)

    Quesada Cabrera, Raul; Firth, Steven; Blackman, Christopher S.; Long, De-Liang; Cronin, Leroy; McMillan, Paul F.

    2012-01-01

    Structural changes occurring within non-conventional Dawson-type [α/β-Mo 18 O 54 (SO 3 ) 2 ] 4− polyanions in the form of tetrapentylammonium salts were studied by a combination of IR, Raman and visible spectroscopy at high temperature and high pressure. Evidence of the formation of bronze-type materials above 400 K and also upon pressurization to 8 GPa is presented. This conclusion is suggested to be a general result for polyoxometalate compounds subjected to extreme conditions and it opens opportunities for the design of new materials with interesting optical and electronic properties. - Graphical abstract: Structural changes occurring within non-conventional Dawson-type [α/β-Mo 18 O 54 (SO 3 ) 2 ] 4− polyanions in the form of tetrapentylammonium salts were studied by a combination of IR, Raman and visible spectroscopy at high temperature and high pressure. Evidence of the formation of bronze-type materials above 400 K and also upon pressurization to 8 GPa is presented. This conclusion is suggested to be a general result for polyoxometalate compounds subjected to extreme conditions and it opens opportunities for the design of new materials with interesting optical and electronic properties. Highlights: ► Spectroscopy studies of non-conventional Wells–Dawson polyoxometalates (POMs) at high temperature and high pressure. ► Discussion on the stability of two POM isomers. ► Local formation of bronze-like materials: possibilities for a new synthetic method at high pressure from POM precursors.

  4. A Styrene-alt-Maleic Acid Copolymer Is an Effective Inhibitor of R5 and X4 Human Immunodeficiency Virus Type 1 Infection

    Directory of Open Access Journals (Sweden)

    Vanessa Pirrone

    2010-01-01

    Full Text Available An alternating copolymer of styrene and maleic acid (alt-PSMA differs from other polyanionic antiviral agents in that the negative charges of alt-PSMA are provided by carboxylic acid groups instead of sulfate or sulfonate moieties. We hypothesized that alt-PSMA would have activity against human immunodeficiency virus type 1 (HIV-1 comparable to other polyanions, such as the related compound, poly(sodium 4-styrene sulfonate (PSS. In assays using cell lines and primary immune cells, alt-PSMA was characterized by low cytotoxicity and effective inhibition of infection by HIV-1 BaL and IIIB as well as clinical isolates of subtypes A, B, and C. In mechanism of action assays, in which each compound was added to cells and subsequently removed prior to HIV-1 infection (“washout” assay, alt-PSMA caused no enhancement of infection, while PSS washout increased infection 70% above control levels. These studies demonstrate that alt-PSMA is an effective HIV-1 inhibitor with properties that warrant further investigation.

  5. Film Self-Assembly of Oppositely Charged Macromolecules Triggered by Electrochemistry through a Morphogenic Approach.

    Science.gov (United States)

    Dochter, Alexandre; Garnier, Tony; Pardieu, Elodie; Chau, Nguyet Trang Thanh; Maerten, Clément; Senger, Bernard; Schaaf, Pierre; Jierry, Loïc; Boulmedais, Fouzia

    2015-09-22

    The development of new surface functionalization methods that are easy to use, versatile, and allow local deposition represents a real scientific challenge. Overcoming this challenge, we present here a one-pot process that consists in self-assembling, by electrochemistry on an electrode, films made of oppositely charged macromolecules. This method relies on a charge-shifting polyanion, dimethylmaleic-modified poly(allylamine) (PAHd), that undergoes hydrolysis at acidic pH, leading to an overall switching of its charge. When a mixture of the two polyanions, PAHd and poly(styrenesulfonate) (PSS), is placed in contact with an electrode, where the pH is decreased locally by electrochemistry, the transformation of PAHd into a polycation (PAH) leads to the continuous self-assembly of a nanometric PAH/PSS film by electrostatic interactions. The pH decrease is obtained by the electrochemical oxidation of hydroquinone, which produces protons locally over nanometric distances. Using a negatively charged enzyme, alkaline phosphatase (AP), instead of PSS, this one-pot process allows the creation of enzymatically active films. Under mild conditions, self-assembled PAH/AP films have an enzymatic activity which is adjustable simply by controlling the self-assembly time. The selective functionalization of microelectrode arrays by PAH/AP was achieved, opening the route toward miniaturized biosensors.

  6. First-principles study of the structural and dynamic properties of the liquid and amorphous Li–Si alloys

    Energy Technology Data Exchange (ETDEWEB)

    Chiang, Han-Hsin; Kuo, Chin-Lung, E-mail: chinlung@ntu.edu.tw [Department of Materials Science and Engineering, National Taiwan University, Taipei 10617, Taiwan (China); Lu, Jian-Ming [National Center for High-Performance Computing, Tainan 74147, Taiwan (China)

    2016-01-21

    We have performed density functional theory calculations and ab initio molecular dynamics to investigate the structures and dynamic properties of the liquid and amorphous Li{sub x}Si alloys over a range of composition from x = 1.0 − 4.8. Our results show that Si atoms can form a variety of covalently bonded polyanions with diverse local bonding structures in the liquid alloys. Like in c-LiSi, Si atoms can form a continuous bond network in liquid Li{sub 1.0}Si at 1050 K, while it gradually disintegrates into many smaller Si polyanions as the Li content increases in the alloys. The average sizes of Si polyanions in these liquid alloys were found to be relatively larger than those in their crystalline counterparts, which can even persist in the highly lithiated Li{sub 4.81}Si alloy at 1500 K. Our results also show that amorphous Li{sub x}Si alloys have similar local bonding structures but a largely increased short-range order as compared to their liquid counterparts. The differences between the average coordination number of each atomic pair in amorphous solids and that in the liquids are less than 1.1. Furthermore, our calculations reveal that Li and Si atoms can exhibit very distinct dynamic behaviors in the liquids and their diffusivities appear to be largely dependent on the chemical composition of the alloys. The diffusivity of Li was found to increase with the Li content in the alloys primarily because of the reduced interactions between Li and Si atoms, while the Si diffusivity also increases due to the gradual disintegration of the strongly interconnected Si bond network. The diffusivity of Li in amorphous Li{sub x}Si was predicted to lie in the range between 10{sup −7} and 10{sup −9} cm{sup 2}/s at 300 K, which is more than 20-fold larger than that of Si over the composition range considered. Our calculations further show that the diffusivities of both Li and Si can increase by two orders of magnitude as x increases from 1.0 to 3.57 in amorphous Li

  7. Crystal Structure, Spectroscopic Investigations, and Physical Properties of the Ternary Intermetallic REPt2Al3 (RE = Y, Dy–Tm and RE2Pt3Al4 Representatives (RE = Tm, Lu

    Directory of Open Access Journals (Sweden)

    Fabian Eustermann

    2018-04-01

    Full Text Available The REPt2Al3 compounds of the late rare-earth metals (RE = Y, Dy–Tm were found to crystallize isostructural. Single-crystal X-ray investigations of YPt2Al3 revealed an orthorhombic unit cell (a = 1080.73(6, b = 1871.96(9, c = 413.04(2 pm, wR2 = 0.0780, 942 F2 values, 46 variables with space group Cmmm (oC48; q2pji2hedb. A comparison with the Pearson database indicated that YPt2Al3 forms a new structure type, in which the Pt and Al atoms form a [Pt2Al3]δ− polyanion and the Y atoms reside in the cavities within the framework. Via a group-subgroup scheme, the relationship between the PrNi2Al3-type structure and the new YPt2Al3-type structure was illustrated. The compounds with RE = Dy–Tm were characterized by powder X-ray diffraction experiments. While YPt2Al3 is a Pauli-paramagnet, the other REPt2Al3 (RE = Dy–Tm compounds exhibit paramagnetic behavior, which is in line with the rare-earth atoms being in the trivalent oxidation state. DyPt2Al3 and TmPt2Al3 exhibit ferromagnetic ordering at TC = 10.8(1 and 4.7(1 K and HoPt2Al3 antiferromagnetic ordering at TN = 5.5(1 K, respectively. Attempts to synthesize the isostructural lutetium compound resulted in the formation of Lu2Pt3Al4 (Ce2Ir3Sb4-type, Pnma, a = 1343.4(2, b = 416.41(8, c = 1141.1(2 pm, which could also be realized with thulium. The structure was refined from single-crystal data (wR2 = 0.0940, 1605 F2 values, 56 variables. Again, a polyanion with bonding Pt–Al interactions was found, and the two distinct Lu atoms were residing in the cavities of the [Pt3Al4]δ– framework. X-ray photoelectron spectroscopy (XPS measurements were conducted to examine the electron transfer from the rare-earth atoms onto the polyanionic framework.

  8. Ein «Gemeinschaftsgrab» für tote aus der Varusschlacht im Südlichen Hispanien? - Zur frühneuzeitlichen Uberleieferung Zweier Inschrifien und Grabepigramme

    Directory of Open Access Journals (Sweden)

    Wiegels, Rainer

    2001-12-01

    Full Text Available Two Roman inscriptions are supposed to have been discovered at "Hellerena", modern Llerena in southern Spain, to which were often, but not always added epigrams. The same inscriptions are also recorded to have been found at the Lower Rhine near Castra Vetera I/Xanten. The obvious spurious inscriptions, which are only mentioned in manuscripts, are about a polyandreîon in which soldiers of the legio V and XIX were buried, who had been killed in action while defending Castra Vetera. Furthermore they tell us about bones of the dead of the same legions in the Varus-battle A.D. 9, that Germanicus ordered to be buried. The paper tries to solve the problem of the unusual tradition of the inscriptions. The arrangement of the two legions probably goes back to a certain early version of Tacitus' acute Annals.Dos inscripciones romanas se descubrieron supuestamente en "Hellerena", la actual Llerena en el Sur de España, a las que se añadieron algunos epigramas. Estas mismas inscripciones se mencionan como hallazgos de las cercanías de Vetera I/Xanten, en el bajo Rhin. Las inscripciones, claramente espúreas y mencionadas solamente en manuscritos, tratan de los "polyandreîon" en los que los soldados de las legiones V y XIX fueron enterrados tras su muerte defendiendo los Castra Vetera. Estos manuscritos cuentan incluso que Germánico, más tarde, mandó enterrar huesos de otros soldados de esas mismas legiones caídos en la clades Variana del 9 d.C. Este artículo intenta resolver el problema de esta tradición literaria inusual de las inscripciones. El falso procede posiblemente de una antigua versión de los precisos Anales de Tácito.

  9. Copper in soil fractions and runoff in a vineyard catchment: Insights from copper stable isotopes.

    Science.gov (United States)

    Babcsányi, Izabella; Chabaux, François; Granet, Mathieu; Meite, Fatima; Payraudeau, Sylvain; Duplay, Joëlle; Imfeld, Gwenaël

    2016-07-01

    Understanding the fate of copper (Cu) fungicides in vineyard soils and catchments is a prerequisite to limit the off-site impact of Cu. Using Cu stable isotopes, Cu retention in soils and runoff transport was investigated in relation to the use of Cu fungicides and the hydrological conditions in a vineyard catchment (Rouffach, Haut-Rhin, France; mean slope: 15%). The δ(65)Cu values of the bulk vineyard soil varied moderately through the depth of the soil profiles (-0.12 to 0.24‰±0.08‰). The values were in the range of those of the fungicides (-0.21 to 0.11‰) and included the geogenic δ(65)Cu value of the untreated soil (0.08‰). However, δ(65)Cu values significantly differed between particle-size soil fractions (-0.37±0.10‰ in fine clays and 0.23±0.07‰ in silt). Together with the soil mineralogy, the results suggested Cu isotope fractionation primarily associated with the clay and fine clay fractions that include both SOM and mineral phases. The vegetation did not affect the Cu isotope patterns in the vineyard soils. Cu export by runoff from the catchment accounted for 1% of the applied Cu mass from 11th May to 20(th) July 2011, covering most of the Cu use period. 84% of the exported Cu mass was Cu bound to suspended particulate matter (SPM). The runoff displayed δ(65)Cu values from 0.52 to 1.35‰ in the dissolved phase (runoff. Overall, this study shows that Cu stable isotopes may allow identifying the Cu distribution in the soil fractions and their contribution to Cu export in runoff from Cu-contaminated catchments. Copyright © 2016 Elsevier B.V. All rights reserved.

  10. Déclin et restauration de la population de truites lacustres (Salmo trutta lacustris L. du lac de Constance

    Directory of Open Access Journals (Sweden)

    RUHLÉ C.

    1990-10-01

    Full Text Available Le déclin de la population de truites migratrices du lac de Constance a débuté vers 1950 quand un barrage a été construit sur le Rhin, affluent principal de ce lac, coupant ainsi l'accès aux plus importantes frayères. Ceci a suffi de prétexte pour renoncer à une longueur de capture garantissant la reproduction naturelle. Par la suite, la population en train de diminuer a servi de justification pour des déversements importants de truites arc-en-ciel. Un désintérêt croissant pour le maintien de frayères dans les affluents secondaires a, finalement, contribué à la baisse des captures de 12.000 kg à 3.000 kg entre 1950 et 1980.Les mesures réalisées au cours des dernières années pour restaurer la population de truites lacustres ont du succès. Il s'agit surtout de : — la détermination d'une nouvelle longueur de capture ainsi que de périodes de protection respectant la reproduction des truites migrant à longue et à courte distance,— l'élevage de stocks de géniteurs, — les déversements forcés et effectués surtout en affluents (au lieu du lac,— l'interdiction d'immersions de truites arc-en-ciel,— l'abolition de barrages. Le succès se manifeste par un nombre croissant de truites observées frayant dans les affluents ainsi que par des captures de plus en plus nombreuses faites par la pêche professionnelle.

  11. Pesticide fate on catchment scale: conceptual modelling of stream CSIA data

    Science.gov (United States)

    Lutz, Stefanie R.; van der Velde, Ype; Elsayed, Omniea F.; Imfeld, Gwenaël; Lefrancq, Marie; Payraudeau, Sylvain; van Breukelen, Boris M.

    2017-10-01

    Compound-specific stable isotope analysis (CSIA) has proven beneficial in the characterization of contaminant degradation in groundwater, but it has never been used to assess pesticide transformation on catchment scale. This study presents concentration and carbon CSIA data of the herbicides S-metolachlor and acetochlor from three locations (plot, drain, and catchment outlets) in a 47 ha agricultural catchment (Bas-Rhin, France). Herbicide concentrations at the catchment outlet were highest (62 µg L-1) in response to an intense rainfall event following herbicide application. Increasing δ13C values of S-metolachlor and acetochlor by more than 2 ‰ during the study period indicated herbicide degradation. To assist the interpretation of these data, discharge, concentrations, and δ13C values of S-metolachlor were modelled with a conceptual mathematical model using the transport formulation by travel-time distributions. Testing of different model setups supported the assumption that degradation half-lives (DT50) increase with increasing soil depth, which can be straightforwardly implemented in conceptual models using travel-time distributions. Moreover, model calibration yielded an estimate of a field-integrated isotopic enrichment factor as opposed to laboratory-based assessments of enrichment factors in closed systems. Thirdly, the Rayleigh equation commonly applied in groundwater studies was tested by our model for its potential to quantify degradation on catchment scale. It provided conservative estimates on the extent of degradation as occurred in stream samples. However, largely exceeding the simulated degradation within the entire catchment, these estimates were not representative of overall degradation on catchment scale. The conceptual modelling approach thus enabled us to upscale sample-based CSIA information on degradation to the catchment scale. Overall, this study demonstrates the benefit of combining monitoring and conceptual modelling of concentration

  12. L’école historique française du droit a-t-elle existé?

    Directory of Open Access Journals (Sweden)

    Philippe Sturmel

    2002-01-01

    Full Text Available Jourdan ou Klimrath, émules français de Savigny dans la première moitié du XIXe siècle, sont des noms que les historiens du droit connaissent bien. Mais cela a-t-il toujours été le cas et surtout quelle a été la portée de leur action scientifique au XIXe siècle? Ce sont ces questions auxquelles l’article tente de répondre et cela de deux points de vue: d’une part en examinant la réception en France des thèses de ce que l’on a appelé l’Ecole historique française dans un temps où l’Ecole de l’exégèse exerce une domination sans partage; d’autre part, en observant les réactions allemandes devant cette production juridique historique française qui s’inscrit dans le courant savignien, observation basée notamment sur le dépouillement exhaustif de la Kritische Zeitschrift für Rechtswissenschaft und Gesetzgebung des Auslandes dirigée par Mittermaier. Que constate-t-on? Des deux côtés du Rhin, l’Ecole historique française a été étouffée. Ici, ses adeptes étaient accusés de pro germanisme; là, ils n’étaient finalement que les disciples de Savigny. Et pourtant leur action en faveur des sciences juridique et historique mérite pleinement qu’on voie en eux les fondateurs d’une véritable Ecole historique française du droit.

  13. Conductometric investigation of salt-free solutions of polyriboguanylic acid. Issledovanie bessolevykh rastvorov poliriboguanilovoj kisloty metodom konduktometrii

    Energy Technology Data Exchange (ETDEWEB)

    Kozlov, A G; Davydova, O V; Kargov, S I [Moskovskij Gosudarstvennyj Univ., Moscow (Russian Federation). Khimicheskij Fakul' tet

    1993-08-01

    Salt-free solutions of various ionic forms of polyriboguanylic acid (poly(G)) were studied by the methods of conductometry and spectroscopy of annular dichroism. The Manning approach was employed to calculate transport characteristics and structural parameters of poly(G) on the basis of spectra permit putting poly(G) salts in two groups: the first one comprising NH[sub 4][sup +]-, Rb[sup +]-, K[sup +]-, Na[sup +]-, the second one - Cs[sup +]-, and Li[sup +]-poly(G). The assumption is made that Li[sup +] and Cs[sup +] ions, bound with concrete groups of polyanion in a specific way, can promote formation of a stable structure different from the one observed in the presence of the first group counterions. 25 refs., 3 figs.

  14. Conductometric investigation of salt-free solutions of polyriboguanylic acid

    International Nuclear Information System (INIS)

    Kozlov, A.G.; Davydova, O.V.; Kargov, S.I.

    1993-01-01

    Salt-free solutions of various ionic forms of polyriboguanylic acid (poly(G)) were studied by the methods of conductometry and spectroscopy of annular dichroism. The Manning approach was employed to calculate transport characteristics and structural parameters of poly(G) on the basis of spectra permit putting poly(G) salts in two groups: the first one comprising NH 4 + -, Rb + -, K + -, Na + -, the second one - Cs + -, and Li + -poly(G). The assumption is made that Li + and Cs + ions, bound with concrete groups of polyanion in a specific way, can promote formation of a stable structure different from the one observed in the presence of the first group counterions. 25 refs., 3 figs

  15. Lipid phase control of DNA delivery

    Energy Technology Data Exchange (ETDEWEB)

    Koynova, Rumiana; Wang, Li; Tarahovsky, Yury; MacDonald, Robert C. (NWU)

    2010-01-18

    Cationic lipids form nanoscale complexes (lipoplexes) with polyanionic DNA and can be utilized to deliver DNA to cells for transfection. Here we report the correlation between delivery efficiency of these DNA carriers and the mesomorphic phases they form when interacting with anionic membrane lipids. Specifically, formulations that are particularly effective DNA carriers form phases of highest negative interfacial curvature when mixed with anionic lipids, whereas less effective formulations form phases of lower curvature. Structural evolution of the carrier lipid/DNA complexes upon interaction with cellular lipids is hence suggested as a controlling factor in lipid-mediated DNA delivery. A strategy for optimizing lipofection is deduced. The behavior of a highly effective lipoplex formulation, DOTAP/DOPE, is found to conform to this 'efficiency formula'.

  16. Covalently attached multilayer assemblies of diazo-resins and binuclear cobalt phthalocyanines

    International Nuclear Information System (INIS)

    Li Xiaofang; Zhao Shuang; Yang Min; Sun Changqing; Guo, Liping

    2005-01-01

    By using the ionic self-assembly technique, ordered multilayer thin films composed of diazo-resin (DAR) as polycation and water-soluble binuclear cobalt phthalocyaninehexasulfonate (Bi-CoPc) as polyanion were alternately fabricated on quartz, CaF 2 and glassy carbon electrodes (GCEs). Upon ultraviolet irradiation, the adjacent interface of the multilayer films reacted to form a covalently cross-linking structure. The obtained thin films were characterized by ultraviolet (UV)-vis, Fourier transform infrared spectrometer (FTIR), X-ray diffraction (XRD), atomic force microscope (AFM), surface photovoltage spectra (SPS), and cyclic voltammetry. The results show that the uniform, highly stable and ordered multilayer thin films were formed. The linkage nature between the adjacent interface of the multilayer films converts from ionic to covalent, and, as a result, the stability of the multilayer thin films dramatically improved. The multilayer thin films on GCEs also exhibited excellent electrochemical behavior

  17. Covalently attached multilayer assemblies of diazo-resins and binuclear cobalt phthalocyanines

    Energy Technology Data Exchange (ETDEWEB)

    Li Xiaofang [Key Lab of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130023 (China); Zhao Shuang [Key Lab of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130023 (China); Yang Min [Key Lab of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130023 (China); Sun Changqing [Key Lab of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130023 (China)]. E-mail: sunchq@mail.jlu.edu.cn; Guo, Liping [Department of Chemistry, Northeast Normal University, Changchun 130024 (China)

    2005-05-01

    By using the ionic self-assembly technique, ordered multilayer thin films composed of diazo-resin (DAR) as polycation and water-soluble binuclear cobalt phthalocyaninehexasulfonate (Bi-CoPc) as polyanion were alternately fabricated on quartz, CaF{sub 2} and glassy carbon electrodes (GCEs). Upon ultraviolet irradiation, the adjacent interface of the multilayer films reacted to form a covalently cross-linking structure. The obtained thin films were characterized by ultraviolet (UV)-vis, Fourier transform infrared spectrometer (FTIR), X-ray diffraction (XRD), atomic force microscope (AFM), surface photovoltage spectra (SPS), and cyclic voltammetry. The results show that the uniform, highly stable and ordered multilayer thin films were formed. The linkage nature between the adjacent interface of the multilayer films converts from ionic to covalent, and, as a result, the stability of the multilayer thin films dramatically improved. The multilayer thin films on GCEs also exhibited excellent electrochemical behavior.

  18. Design of Chitosan and Its Water Soluble Derivatives-Based Drug Carriers with Polyelectrolyte Complexes

    Directory of Open Access Journals (Sweden)

    Qing-Xi Wu

    2014-12-01

    Full Text Available Chitosan, the cationic polysaccharide derived from the natural polysaccharide chitin, has been studied as a biomaterial for more than two decades. As a polycationic polymer with favorable properties, it has been widely used to form polyelectrolyte complexes with polyanions for various applications in drug delivery fields. In recent years, a growing number of studies have been focused on the preparation of polyelectrolyte complexes based on chitosan and its water soluble derivatives. They have been considered well-suited as biomaterials for a number of vital drug carriers with targeted/controlled release profiles, e.g., films, capsules, microcapsules. In this work, an overview highlights not only the favorable properties of chitosan and its water soluble derivatives but also the good performance of the polyelectrolyte complexes produced based on chitosan. Their various types of applications as drug carriers are reviewed in detail.

  19. Design of chitosan and its water soluble derivatives-based drug carriers with polyelectrolyte complexes.

    Science.gov (United States)

    Wu, Qing-Xi; Lin, Dong-Qiang; Yao, Shan-Jing

    2014-12-19

    Chitosan, the cationic polysaccharide derived from the natural polysaccharide chitin, has been studied as a biomaterial for more than two decades. As a polycationic polymer with favorable properties, it has been widely used to form polyelectrolyte complexes with polyanions for various applications in drug delivery fields. In recent years, a growing number of studies have been focused on the preparation of polyelectrolyte complexes based on chitosan and its water soluble derivatives. They have been considered well-suited as biomaterials for a number of vital drug carriers with targeted/controlled release profiles, e.g., films, capsules, microcapsules. In this work, an overview highlights not only the favorable properties of chitosan and its water soluble derivatives but also the good performance of the polyelectrolyte complexes produced based on chitosan. Their various types of applications as drug carriers are reviewed in detail.

  20. The guanidinium group as a key part of water-soluble polymer carriers for siRNA complexation and protection against degradation.

    Science.gov (United States)

    Tabujew, Ilja; Freidel, Christoph; Krieg, Bettina; Helm, Mark; Koynov, Kaloian; Müllen, Klaus; Peneva, Kalina

    2014-07-01

    Here, the preparation of a novel block copolymer consisting of a statistical copolymer N-(2-hydroxypropyl) methacrylamide-s-N-(3-aminopropyl) methacrylamide and a short terminal 3-guanidinopropyl methacrylamide block is reported. This polymer structure forms neutral but water-soluble nanosized complexes with siRNA. The siRNA block copolymer complexes are first analyzed using agarose gel electrophoresis and their size is determined with fluorescence correlation spectroscopy. The protective properties of the polymer against RNA degradation are investigated by treating the siRNA block copolymer complexes with RNase V1. Heparin competition assays confirm the efficient release of the cargo in vitro. In addition, the utilization of microscale thermophoresis is demonstrated for the determination of the binding strength between a fluorescently labeled polyanion and a polymer molecule. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Hydrogel Walkers with Electro-Driven Motility for Cargo Transport.

    Science.gov (United States)

    Yang, Chao; Wang, Wei; Yao, Chen; Xie, Rui; Ju, Xiao-Jie; Liu, Zhuang; Chu, Liang-Yin

    2015-08-28

    In this study, soft hydrogel walkers with electro-driven motility for cargo transport have been developed via a facile mould-assisted strategy. The hydrogel walkers consisting of polyanionic poly(2-acrylamido-2-methylpropanesulfonic acid-co-acrylamide) exhibit an arc looper-like shape with two "legs" for walking. The hydrogel walkers can reversibly bend and stretch via repeated "on/off" electro-triggers in electrolyte solution. Based on such bending/stretching behaviors, the hydrogel walkers can move their two "legs" to achieve one-directional walking motion on a rough surface via repeated "on/off" electro-triggering cycles. Moreover, the hydrogel walkers loaded with very heavy cargo also exhibit excellent walking motion for cargo transport. Such hydrogel systems create new opportunities for developing electro-controlled soft systems with simple design/fabrication strategies in the soft robotic field for remote manipulation and transportation.

  2. An Oxygen-Insensitive Hydrogen Evolution Catalyst Coated by a Molybdenum-Based Layer for Overall Water Splitting

    KAUST Repository

    Garcia Esparza, Angel T.; Shinagawa, Tatsuya; Ould-Chikh, Samy; Qureshi, Muhammad; Peng, Xuyuan; Wei, Nini; Anjum, Dalaver H.; Clo, Alain M.; Weng, Tsu-Chien; Nordlund, Dennis; Sokaras, Dimosthenis; Kubota, Jun; Domen, Kazunari; Takanabe, Kazuhiro

    2017-01-01

    For overall water-splitting systems, it is essential to establish O2 -insensitive cathodes that allow cogeneration of H2 and O2 . An acid-tolerant electrocatalyst is described, which employs a Mo-coating on a metal surface to achieve selective H2 evolution in the presence of O2 . In operando X-ray absorption spectroscopy identified reduced Pt covered with an amorphous molybdenum oxyhydroxide hydrate with a local structural order composed of polyanionic trimeric units of molybdenum(IV). The Mo layer likely hinders O2 gas permeation, impeding contact with active Pt. Photocatalytic overall water splitting proceeded using MoOx /Pt/SrTiO3 with inhibited water formation from H2 and O2 , which is the prevailing back reaction on the bare Pt/SrTiO3 photocatalyst. The Mo coating was stable in acidic media for multiple hours of overall water splitting by membraneless electrolysis and photocatalysis.

  3. Influence of ionic strength on the viscosities and water loss of bentonite suspensions containing polymers

    Directory of Open Access Journals (Sweden)

    Luciana Viana Amorim

    2007-03-01

    Full Text Available A study was made of the influence of ionic strength (S on the apparent (AV and plastic (PV viscosities and water loss (WL of sodium bentonite suspension with polymers. Na-bentonite was dispersed in water (4.86% w/w of different ionic strengths (S = 0.0, 0.015, 0.030 and 0.045 M followed by the addition of polymer. Three polymer samples were studied, i.e., low viscosity carboxymethyl cellulose (CMC BV, polyanionic cellulose (PAC, and partially hydrolyzed polyacrylamide (HPAM. The results indicated that the presence of salts and increased salinity greatly influence the apparent and plastic viscosities and water loss of bentonite suspensions with polymer.

  4. Effect of synthetic adjuvants of biological activity of spleen proteins

    International Nuclear Information System (INIS)

    Kartasheva, A.L.; Yuferova, N.V.; Drozhennikov, V.A.; Orlova, E.B.; Perevezentseva, O.S.; Filatov, P.P.

    1981-01-01

    Intraperitoneal administration to mice of synthetic adjuvants of a polyanion type increases the spleen mass by 500% and rises the content of proteins with activity of inhibitor of DNAase 1. A protein fraction isolated from the spleen of treated animals administered to exposed (7.7 Gy) mice alone or in a combination with exogenous DNA increases survival up to 61.1 and 80.5%, respectively, as opposed to 36.6% in the case of administration of proteins from intact animals, or 8.3% in the control (no treatment). The protein fraction from treated animals administered to mice exposed to 5.1-5.5 Gy accelerates the recovery of hemopoesis and immune response better than proteins of intact animals

  5. Synthesis and crystal structure of the rare earth borogermanate EuGeBO{sub 5}

    Energy Technology Data Exchange (ETDEWEB)

    Chi, Yang; Zhuang, Yan; Guo, Sheng-Ping [Yangzhou Univ., Jiangsu (China). College of Chemistry and Chemical Engineering

    2017-03-01

    The synthesis and crystal structure of the rare earth borogermanate EuGeBO{sub 5} are reported. It is synthesized by high-temperature solid-state reaction and crystallizes in the monoclinic space group P2{sub 1}/c (no. 14) with the unit cell parameters a=4.8860(5), b=7.5229(8), c=9.9587(10) Aa, and β=91.709(3) . Its crystal structure features a polyanion-type layer (GeBO{sub 5}){sup 3-} constructed by BO{sub 4} and GeO{sub 4} tetrahedra connected alternatingly. Eu{sup 3+} ions are located in cavities and are coordinated by eight O atoms. Various structures of the related compounds REMM'O{sub 5} (RE=rare earth metal; M=Si, Ge, and Sn; M'=B, Al, and Ga) are also discussed.

  6. Control superstructure of rigid polyelectrolytes in oppositely charged hydrogels via programmed internal stress

    Science.gov (United States)

    Takahashi, Riku; Wu, Zi Liang; Arifuzzaman, Md; Nonoyama, Takayuki; Nakajima, Tasuku; Kurokawa, Takayuki; Gong, Jian Ping

    2014-08-01

    Biomacromolecules usually form complex superstructures in natural biotissues, such as different alignments of collagen fibres in articular cartilages, for multifunctionalities. Inspired by nature, there are efforts towards developing multiscale ordered structures in hydrogels (recognized as one of the best candidates of soft biotissues). However, creating complex superstructures in gels are hardly realized because of the absence of effective approaches to control the localized molecular orientation. Here we introduce a method to create various superstructures of rigid polyanions in polycationic hydrogels. The control of localized orientation of rigid molecules, which are sensitive to the internal stress field of the gel, is achieved by tuning the swelling mismatch between masked and unmasked regions of the photolithographic patterned gel. Furthermore, we develop a double network structure to toughen the hydrogels with programmed superstructures, which deform reversibly under large strain. This work presents a promising pathway to develop superstructures in hydrogels and should shed light on designing biomimetic materials with intricate molecular alignments.

  7. Multilayer Films and Capsules of Sodium Carboxymethylcellulose and Polyhexamethylenguanidine Hydrochloride

    Science.gov (United States)

    Guzenko, Nataliia; Gabchak, Oleksandra; Pakhlov, Evgenij

    The complexation of polyhexamethylenguanidine hydrochloride (PHMG) and sodium carboxymethylcellulose (CMC) was investigated for different conditions. Mixing of equiconcentrated aqueous solutions of the polyelectrolytes was found to result in the formation of an insoluble interpolyelectrolyte complex with an overweight of carboxymethylcellulose. A step-by-step formation of stable, irreversibly adsorbed multilayer film of the polymers was demonstrated using the quartz crystal microbalance method. Unusually thick polymer shells with a large number of loops and tails of the polyanion were formed by the method of layer-by-layer self-assembly of PHMG and CMC on spherical CaCO3 particles. Hollow multilayer capsules stable in neutral media were obtained by dissolution of the inorganic matrix in EDTA solution.

  8. Compaction agent clarification of microbial lysates

    Science.gov (United States)

    DeWalt, Brad W.; Murphy, Jason C.; Fox, George E.; Willson, Richard C.

    2003-01-01

    Recombinant proteins are often purified from microbial lysates containing high concentrations of nucleic acids. Pre-purification steps such as nuclease addition or precipitation with polyethyleneimine or ammonium sulfate are normally required to reduce viscosity and to eliminate competing polyanions before anion exchange chromatography. We report that small polycationic compaction agents such as spermine selectively precipitate nucleic acids during or after Escherichia coli lysis, allowing DNA and RNA to be pelleted with the insoluble cell debris. Analysis by spectrophotometry and protein assay confirmed a significant reduction in the concentration of nucleic acids present, with preservation of protein. Lysate viscosity is greatly reduced, facilitating subsequent processing. We have used 5mM spermine to remove nucleic acids from E. coli lysate in the purification of a hexahistidine-tagged HIV reverse transcriptase.

  9. Effect of anionic polyelectrolytes on the flow of activated sodium bentonite drilling mud

    Directory of Open Access Journals (Sweden)

    Chalah Kaci

    2018-01-01

    Full Text Available Bentonite is often used in water-based drilling fluids. The xanthan gum is widely used as to increase the viscosity of the bentonite suspension. For the stabilization of the drilled layers, we use filtrate reducers: sodium carboxymethylcellulose low viscosity and cellulose polyanionic low viscosity. The objective of this work is to explain the effect of the polymers on the rheological behavior of the 5% bentonite suspensions. These results will provide practical recommendations for the rational use of different types of additives in water-based drilling muds. Our work is based on rheological trials on a viscometer. The results obtained on the bentonite 5%-xanthane suspension show a rheofluidifying behavior with yield stress conform to the Herschel-bulckly modal. While increasing the concentration of filtrate reducer decreases the yield stress and reduces the viscosity. The effect of CMC LV is more pronounced than PAC L.

  10. [Method of multilayer assembly as alternative to antibacterial coverings of medicobiological implants].

    Science.gov (United States)

    Ospanova, A K; Omarova, R A; Abdurazakov, U A; Zhartybaev, R N; Iskakova, M K; Savdenbekova, B E; Amkhadova, M A

    2016-01-01

    Department of Traumatology and Orthopedics Almaty Kazakh Medical University of Continuing Education; 4. Moscow Regional Research Clinical Institute, Russia Resume: in this report we present the results on the use of the method of layer-by-layer (LbL) for obtaining antimicrobial coatings for biomedical implants. As the substrates were used silicon titanium implants and silicon plate. For the obtaining multilayer coatings on the surfaces of the samples were used as the polycation--chitosan and polyanion--carboxymethylcellulose sodium. On the surface multilayer were deposited antibacterial preparations: Triclosan-2,4,4'trichloro-2' hydroxyphenyl ether, silver ions and iodine. Microbiological studies were conducted on the museum strains: E. coli, Candida and Staf. Preliminary antibacterial studies on these microorganisms showed high activity multilayer coating containing triclosan.

  11. In vitro studies of PBT Nonwoven Fabrics adsorbent for the removal of low density lipoprotein from hyperlipemia plasma

    Energy Technology Data Exchange (ETDEWEB)

    Cao Ye; Wang Hong [Institute of Blood Transfusion, Chinese Academy of Medical Sciences and Peking Union Medical College, Chengdu 610052 (China); Yang Chao [State Key Lab of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai 200240 (China); Zhong Rui [Institute of Blood Transfusion, Chinese Academy of Medical Sciences and Peking Union Medical College, Chengdu 610052 (China); Lei Yu [Chengdu Blood Center, Chengdu 610041 (China); Sun Kang [State Key Lab of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai 200240 (China); Liu Jiaxin, E-mail: jxliu8122@vip.sina.com [Institute of Blood Transfusion, Chinese Academy of Medical Sciences and Peking Union Medical College, Chengdu 610052 (China)

    2011-06-15

    Polyanion ligands such as acrylic acid (AA) and heparin were grafted on PBT Nonwoven Fabrics (PBTNF) to study their effect on the adsorption of low density lipoprotein (LDL). These modified PBTNFs were characterized by Horizontal Attenuated Total Reflectance Fourier Transform Infrared spectroscopy and X-ray Photoelectron spectroscopy. The blood compatibilities of the modified PBTNFs were examined using in vitro hemolysis rate (HR), platelet adhesion, total protein (TP) and activated partial thromboplastin time. The results showed that direct immobilized heparin could improve PBTNF-PAA's blood compatibility and decrease the adsorption capability of useful high density lipoprotein, but would possess so low bioactivity that could not further improve the absorption of LDL and TC. Since the PBTNF-PAA55-Heparin adsorbent had quite good adsorption selectivity for these proteins, it can be an excellent candidate for depletion of LDL with good blood compatibility.

  12. Preparation, electrochemical characterization and charge-discharge of reticulated vitreous carbon/polyaniline composite electrodes

    International Nuclear Information System (INIS)

    Dalmolin, Carla; Biaggio, Sonia R.; Rocha-Filho, Romeu C.; Bocchi, Nerilso

    2009-01-01

    Polyaniline was electrodeposited onto reticulated vitreous carbon - RVC - in order to obtain a tridimensional composite electrode. Three variations of these electrodes were analysed: a small-anion-doped polyaniline (RVC/Pani), a polyanion-doped polyaniline (RVC/PaniPSS) and a bi-layer type formed by an inner layer of the first electrode and an outer layer of the second one (RVC/Pani/PaniPSS). These composites were characterized by cyclic voltammetry, scanning electronic microscopy and electrochemical impedance spectroscopy. Photomicrographies, voltammetric profiles and impedance data pointed to different morphological and electrochemical characteristics for polyaniline doped with small or large anions, and a mixed behavior for the bi-layer electrodes. Charge-discharge tests for these tridimensional (3D) electrodes, employed as the cathode in lithium batteries, indicated better performance for the RVC/Pani electrode. These RVC composites presented higher specific capacities when compared with those obtained for Pani deposited onto bidimensional substrates.

  13. Importance of diffuse metal ion binding to RNA.

    Science.gov (United States)

    Tan, Zhi-Jie; Chen, Shi-Jie

    2011-01-01

    RNAs are highly charged polyanionic molecules. RNA structure and function are strongly correlated with the ionic condition of the solution. The primary focus of this article is on the role of diffusive ions in RNA folding. Due to the long-range nature of electrostatic interactions, the diffuse ions can contribute significantly to RNA structural stability and folding kinetics. We present an overview of the experimental findings as well as the theoretical developments on the diffuse ion effects in RNA folding. This review places heavy emphasis on the effect of magnesium ions. Magnesium ions play a highly efficient role in stabilizing RNA tertiary structures and promoting tertiary structural folding. The highly efficient role goes beyond the mean-field effect such as the ionic strength. In addition to the effects of specific ion binding and ion dehydration, ion-ion correlation for the diffuse ions can contribute to the efficient role of the multivalent ions such as the magnesium ions in RNA folding.

  14. Catalytic oxidation of light alkanes (C1-C4) by heteropoly compounds

    KAUST Repository

    Sun, Miao; Zhang, Jizhe; Putaj, Piotr; Caps, Valerie; Lefè bvre, Fré dé ric; Pelletier, Jeremie; Basset, Jean-Marie

    2014-01-01

    Heteropoly compounds (HPC) have revealed their potential to generate catalyst for selectively converting light alkanes to oxygenated products. There are various structures in which they are active the primary structure being that of the heteropolyanion itself, the secondary structure is the three-dimensional arrangements of polyanions, and the tertiary structure representing the manner in which the secondary structure assembles into solid particles. There are also a huge variety of elements inside the HPA. The heteropoly acids can have acidity, which varies dramatically depending on composition. This complexity of situation makes it very difficult to really have a predictive vision of their ability to activate and functionalize alkanes. However, a large amount of data reported suggests that the initial formula of the precatalyst is pivotal to direct the selectivity of the reaction toward different oxygenates. Inclusion of alternative transition metal atoms as addenda is highly influential with iron, vanadium, and antimony being particularly outstanding.

  15. Na2MnSiO4 as an attractive high capacity cathode material for sodium-ion battery

    Science.gov (United States)

    Law, Markas; Ramar, Vishwanathan; Balaya, Palani

    2017-08-01

    Here we report a polyanion-based cathode material for sodium-ion batteries, Na2MnSiO4, registering impressive sodium storage performances with discharge capacity of 210 mAh g-1 at an average voltage of 3 V at 0.1 C, along with excellent long-term cycling stability (500 cycles at 1 C). Insertion/extraction of ∼1.5 mol of sodium ion per formula unit of the silicate-based compound is reported and the utilisation of Mn2+ ⇋ Mn4+ redox couple is also demonstrated by ex-situ XPS. Besides, this study involves a systematic investigation of influence of the electrolyte additive (with different content) on the sodium storage performance of Na2MnSiO4. The electrolyte additive forms an optimum protective passivation film on the electrode surface, successfully reducing manganese dissolution.

  16. RNA folding: structure prediction, folding kinetics and ion electrostatics.

    Science.gov (United States)

    Tan, Zhijie; Zhang, Wenbing; Shi, Yazhou; Wang, Fenghua

    2015-01-01

    Beyond the "traditional" functions such as gene storage, transport and protein synthesis, recent discoveries reveal that RNAs have important "new" biological functions including the RNA silence and gene regulation of riboswitch. Such functions of noncoding RNAs are strongly coupled to the RNA structures and proper structure change, which naturally leads to the RNA folding problem including structure prediction and folding kinetics. Due to the polyanionic nature of RNAs, RNA folding structure, stability and kinetics are strongly coupled to the ion condition of solution. The main focus of this chapter is to review the recent progress in the three major aspects in RNA folding problem: structure prediction, folding kinetics and ion electrostatics. This chapter will introduce both the recent experimental and theoretical progress, while emphasize the theoretical modelling on the three aspects in RNA folding.

  17. Generalized polymer effective charge measurement by capillary isotachophoresis.

    Science.gov (United States)

    Chamieh, Joseph; Koval, Dušan; Besson, Adeline; Kašička, Václav; Cottet, Hervé

    2014-11-28

    In this work, we have generalized the use of capillary isotachophoresis as a universal method for determination of effective charge of anionic and cationic (co)polymers on ordinary capillary electrophoresis instruments. This method is applicable to a broad range of strong or weak polyelectrolytes with good repeatability. Experimental parameters (components and concentrations of leading and terminating electrolytes, capillary diameters, constant electric current intensity) were optimized for implementation in 100 μm i.d. capillaries for both polyanions and polycations. Determined values of polymer effective charge were in a very good agreement with those obtained by capillary electrophoresis with indirect UV detection. Uncertainty of the effective charge measurement using isotachophoresis was addressed and estimated to be ∼5-10% for solutes with mobilities in the 20-50 × 10(-9)m(2)V(-1)s(-1) range. Copyright © 2014 Elsevier B.V. All rights reserved.

  18. Phosphorus dendrimers and photodynamic therapy. Spectroscopic studies on two dendrimer-photosensitizer complexes: Cationic phosphorus dendrimer with rose bengal and anionic phosphorus dendrimer with methylene blue.

    Science.gov (United States)

    Dabrzalska, Monika; Zablocka, Maria; Mignani, Serge; Majoral, Jean Pierre; Klajnert-Maculewicz, Barbara

    2015-08-15

    Dendrimers due to their unique architecture may play an important role in drug delivery systems including chemotherapy, gene therapy and recently, photodynamic therapy as well. We investigated two dendrimer-photosensitizer systems in context of potential use of these systems in photodynamic therapy. The mixtures of an anionic phosphorus dendrimer of the second generation and methylene blue were studied by UV-vis spectroscopy while that of a cationic phosphorus dendrimer (third generation) and rose bengal were investigated by spectrofluorimetric methods. Spectroscopic analysis of these two systems revealed the formation of dendrimer-photosensitizer complexes via electrostatic interactions as well as π stacking. The stoichiometry of the rose bengal-cationic dendrimer complex was estimated to be 7:1 and 9:1 for the methylene blue-anionic dendrimer complex. The results suggest that these polyanionic or polycationic phosphorus dendrimers can be promising candidates as carriers in photodynamic therapy. Copyright © 2015 Elsevier B.V. All rights reserved.

  19. Heparin/heparan sulfates bind to and modulate neuronal L-type (Cav1.2) voltage-dependent Ca2+ channels

    DEFF Research Database (Denmark)

    Garau, Gianpiero; Magotti, Paola; Heine, Martin

    2015-01-01

    Our previous studies revealed that L-type voltage-dependent Ca2+ channels (Cav1.2 L-VDCCs) are modulated by the neural extracellular matrix backbone, polyanionic glycan hyaluronic acid. Here we used isothermal titration calorimetry and screened a set of peptides derived from the extracellular......M), integrating their enthalpic and entropic binding contributions. Interaction between heparin and recombinant as well as native full-length neuronal Cav1.2α1 channels was confirmed using the heparin–agarose pull down assay. Whole cell patch clamp recordings in HEK293 cells transfected with neuronal Cav1.......2 channels revealed that enzymatic digestion of highly sulfated heparan sulfates with heparinase 1 affects neither voltage-dependence of channel activation nor the level of steady state inactivation, but did speed up channel inactivation. Treatment of hippocampal cultures with heparinase 1 reduced the firing...

  20. X-ray microanalysis of black piedra.

    Science.gov (United States)

    Figueras, M J; Guarro, J

    1997-11-01

    The elements present in the fungal structures produced by Piedraia hortae in vivo and in vitro have been investigated using electron microscopy X-ray microanalysis. Phosphorus, sulphur and calcium were detected in the nodules which developed on hair and on colonies on culture. These elements belong to the extracellular material that compacts the pseudoparenchymatous organization of the fungus. They may be present due to the capacity of melanin-like pigments to sequester ions and/or they may form part of the sulphates and phosphates of the polyanionic mucopolysaccharides that constitute the extracellular material. Environmental contaminants such as aluminium, silicon and iron were detected exclusively on the surface of the nodule. They were deposited or linked to the residual molecules produced during the breakdown of the cuticular keratin. The advantages of these techniques for elucidating the chemical nature of fungal structures are discussed.

  1. Design of Chitosan and Its Water Soluble Derivatives-Based Drug Carriers with Polyelectrolyte Complexes

    Science.gov (United States)

    Wu, Qing-Xi; Lin, Dong-Qiang; Yao, Shan-Jing

    2014-01-01

    Chitosan, the cationic polysaccharide derived from the natural polysaccharide chitin, has been studied as a biomaterial for more than two decades. As a polycationic polymer with favorable properties, it has been widely used to form polyelectrolyte complexes with polyanions for various applications in drug delivery fields. In recent years, a growing number of studies have been focused on the preparation of polyelectrolyte complexes based on chitosan and its water soluble derivatives. They have been considered well-suited as biomaterials for a number of vital drug carriers with targeted/controlled release profiles, e.g., films, capsules, microcapsules. In this work, an overview highlights not only the favorable properties of chitosan and its water soluble derivatives but also the good performance of the polyelectrolyte complexes produced based on chitosan. Their various types of applications as drug carriers are reviewed in detail. PMID:25532565

  2. Detecting Levels of Polyquaternium-10 (PQ-10) via Potentiometric Titration with Dextran Sulphate and Monitoring the Equivalence Point with a Polymeric Membrane-Based Polyion Sensor.

    Science.gov (United States)

    Ferguson, Stephen A; Wang, Xuewei; Meyerhoff, Mark E

    2016-08-07

    Polymeric quaternary ammonium salts (polyquaterniums) have found increasing use in industrial and cosmetic applications in recent years. More specifically, polyquaternium-10 (PQ-10) is routinely used in cosmetic applications as a conditioner in personal care product formulations. Herein, we demonstrate the use of potentiometric polyion-sensitive polymeric membrane-based electrodes to quantify PQ-10 levels. Mixtures containing both PQ-10 and sodium lauryl sulfate (SLS) are used as model samples to illustrate this new method. SLS is often present in cosmetic samples that contain PQ-10 (e.g., shampoos, etc.) and this surfactant species interferes with the polyion sensor detection chemistry. However, it is shown here that SLS can be readily separated from the PQ-10/SLS mixture by use of an anion-exchange resin and that the PQ-10 can then be titrated with dextran sulphate (DS). This titration is monitored by potentiometric polyanion sensors to provide equivalence points that are directly proportional to PQ-10 concentrations.

  3. Antiviral Activity of Polyacrylic and Polymethacrylic Acids

    Science.gov (United States)

    De Somer, P.; De Clercq, E.; Billiau, A.; Schonne, E.; Claesen, M.

    1968-01-01

    Polyacrylic acid (PAA) and polymethacrylic acid (PMAA) were investigated for their antiviral properties in tissue culture. Compared to other related polyanions, as dextran sulfate, polystyrene sulfonate, polyvinyl sulfate, and polyphloroglucinol phosphate, PAA and PMAA were found to be significantly more antivirally active and less cytotoxic. PMAA added 24 hr prior to virus inoculation inhibited viral growth most efficiently but it was still effective when added 3 hr after infection. Neither a direct irreversible action on the virus nor inhibition of virus penetration into the cell could explain the antiviral activity of PMAA. PMAA inhibited the adsorption of the virus to the host cell and suppressed the one-cycle viral synthesis in tissue cultures inoculated with infectious RNA. PMID:4302187

  4. Comparison of secondary ion emission induced in silicon oxide by MeV and KeV ion bombardment

    International Nuclear Information System (INIS)

    Allali, H.; Nsouli, B.; Thomas, J.P.; Szymczak, W.; Wittmaack, K.

    1993-09-01

    The surface and near-surface composition of SiO 2 layers, has been investigated by negative secondary ion emission mass spectrometry (SIMS) using MeV and KeV ion bombardment in combination with time-of-flight (TOF) mass analysis. The spectra recorded in the mass range 0-100 u are dominated by surface impurities, notably hydrocarbons and silicon polyanions incorporating H and OH entities. The characteristic (fragmentation) patterns are quite different for light and high-velocity ion impact. In high-velocity TOF-SIMS analysis of P-doped layers, prepared by chemical vapour deposition (CVD), the mass lines at 63 and 79 u are very prominent and appear to correlate with the phosphorus concentration (PO 2 and PO 3 , respectively). It is shown, however, that for unambiguous P analysis one has to use dynamic SIMS or high mass resolution. (author) 11 refs., 5 figs

  5. Aggregation of Heteropolyanions Implicates the Presence of Zundel Ions Near Air-Water Interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Bera, Mrinal K. [Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne Illinois 60439 United States; DUBBLE-CRG, ESRF-The European Synchrotron Radiation Facility CS40220, 38043 Grenoble Cedex 9 France; Antonio, Mark R. [Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne Illinois 60439 United States

    2016-07-01

    Protons play crucial roles in the interactions between hetero-polyanions (HPAs) in aqueous solutions and solid acid salts. We report the aggregation behaviours of Keggin HPAs near the surfaces of heteropolyacid solutions. The structure of the aggregated HPA layer near the solution-vapour phase boundary closely resembles the solid-state crystal structure of the hetero-polyacids in which the HPAs are connected by Zundel ions. The resemblance not only implicates the presence of protons in the form of planar Zundel ions near the air-water interface but, also, suggests that these align parallel to the interface. This study demonstrates an indirect means of assessing the impact of protons on HPA interactions near air-water interfaces and, in general, provides new insights about interfacial proton chemistry of heteropolyacids.

  6. An Oxygen-Insensitive Hydrogen Evolution Catalyst Coated by a Molybdenum-Based Layer for Overall Water Splitting

    KAUST Repository

    Garcia Esparza, Angel T.

    2017-04-13

    For overall water-splitting systems, it is essential to establish O2 -insensitive cathodes that allow cogeneration of H2 and O2 . An acid-tolerant electrocatalyst is described, which employs a Mo-coating on a metal surface to achieve selective H2 evolution in the presence of O2 . In operando X-ray absorption spectroscopy identified reduced Pt covered with an amorphous molybdenum oxyhydroxide hydrate with a local structural order composed of polyanionic trimeric units of molybdenum(IV). The Mo layer likely hinders O2 gas permeation, impeding contact with active Pt. Photocatalytic overall water splitting proceeded using MoOx /Pt/SrTiO3 with inhibited water formation from H2 and O2 , which is the prevailing back reaction on the bare Pt/SrTiO3 photocatalyst. The Mo coating was stable in acidic media for multiple hours of overall water splitting by membraneless electrolysis and photocatalysis.

  7. A [Mo{sub 2}O{sub 2}S{sub 2}]-based ring system incorporating tartrate as the bridging ligand. Synthesis, structure and catalytic activity of Cs{sub 4}[Mo{sub 2}O{sub 2}(μ-S){sub 2}]{sub 2}(μ{sub 4}-tart){sub 2} (tart=[C{sub 4}H{sub 2}O{sub 6}]{sup 4-})

    Energy Technology Data Exchange (ETDEWEB)

    Qian, Ting-Ting; Cui, Yu-Jie; Xin, Zhifeng; Jia, Ai-Quan; Zhang, Qian-Feng [Anhui Univ. of Technology, Anhui (China). Inst. of Molecular Engineering and Applied Chemistry and Anhui Province Key Lab. of Metallurgy Engineering and Resources Recycling

    2017-08-01

    Treatment of [Mo{sub 2}S{sub 2}O{sub 2}(H{sub 2}O){sub 6}]{sup 2+} with racemic tartaric acid (tartH{sub 4}) in the presence of sodium hydroxide and cesium chloride in aqueous solution led to the isolation of a new tetra-molybdenum ring cluster Cs{sub 4}[Mo{sub 2}O{sub 2}(μ-S){sub 2}]{sub 2}(μ{sub 4}-tart){sub 2}. The cyclic cluster polyanion consists of two dinuclear [Mo{sub 2}O{sub 2}(μ-S){sub 2}]{sup 2+} moieties and two bridging tart{sup 4-} ligands. The cyclic polyoxothiomolybdate cluster, supported on the mesoporous silica SBA-15, was tested for heterogenerous catalysis in thiophene hydrodesulfurization.

  8. Catalytic oxidation of light alkanes (C1-C4) by heteropoly compounds

    KAUST Repository

    Sun, Miao

    2014-01-22

    Heteropoly compounds (HPC) have revealed their potential to generate catalyst for selectively converting light alkanes to oxygenated products. There are various structures in which they are active the primary structure being that of the heteropolyanion itself, the secondary structure is the three-dimensional arrangements of polyanions, and the tertiary structure representing the manner in which the secondary structure assembles into solid particles. There are also a huge variety of elements inside the HPA. The heteropoly acids can have acidity, which varies dramatically depending on composition. This complexity of situation makes it very difficult to really have a predictive vision of their ability to activate and functionalize alkanes. However, a large amount of data reported suggests that the initial formula of the precatalyst is pivotal to direct the selectivity of the reaction toward different oxygenates. Inclusion of alternative transition metal atoms as addenda is highly influential with iron, vanadium, and antimony being particularly outstanding.

  9. Cationic lipids: molecular structure/ transfection activity relationships and interactions with biomembranes.

    Science.gov (United States)

    Koynova, Rumiana; Tenchov, Boris

    2010-01-01

    Abstract Synthetic cationic lipids, which form complexes (lipoplexes) with polyanionic DNA, are presently the most widely used constituents of nonviral gene carriers. A large number of cationic amphiphiles have been synthesized and tested in transfection studies. However, due to the complexity of the transfection pathway, no general schemes have emerged for correlating the cationic lipid chemistry with their transfection efficacy and the approaches for optimizing their molecular structures are still largely empirical. Here we summarize data on the relationships between transfection activity and cationic lipid molecular structure and demonstrate that the transfection activity depends in a systematic way on the lipid hydrocarbon chain structure. A number of examples, including a large series of cationic phosphatidylcholine derivatives, show that optimum transfection is displayed by lipids with chain length of approximately 14 carbon atoms and that the transfection efficiency strongly increases with increase of chain unsaturation, specifically upon replacement of saturated with monounsaturated chains.

  10. Synthesis and Characterization of 8-Yttrium(III-Containing 81-Tungsto-8-Arsenate(III, [Y8(CH3COO(H2O18(As2W19O684(W2O62(WO4]43−

    Directory of Open Access Journals (Sweden)

    Masooma Ibrahim

    2015-06-01

    Full Text Available The 8-yttrium(III-containing 81-tungsto-8-arsenate(III [Y8(CH3COO(H2O18(As2W19O684(W2O62(WO4]43− (1 has been synthesized in a one-pot reaction of yttrium(III ions with [B-α-AsW9O33]9− in 1 M NaOAc/HOAc buffer at pH 4.8. Polyanion 1 is composed of four {As2W19O68} units, two {W2O10} fragments, one {WO6} group, and eight YIII ions. The hydrated cesium-sodium salt of 1 (CsNa-1 was characterized in the solid-state by single-crystal XRD, FT-IR spectroscopy, thermogravimetric and elemental analyses.

  11. Improved DNA electrophoresis in conditions favoring polyborates and lewis acid complexation.

    Directory of Open Access Journals (Sweden)

    Hari Singhal

    2010-06-01

    Full Text Available Spatial compression among the longer DNA fragments occurs during DNA electrophoresis in agarose and non-agarose gels when using certain ions in the conductive buffer, impairing the range of fragment sizes resolved well in a single gel. Substitutions using various polyhydroxyl anions supported the underlying phenomenon as the complexation of Lewis acids to DNA. We saw significant improvements using conditions (lithium borate 10 mM cations, pH 6.5 favoring the formation of borate polyanions and having lower conductance and Joule heating, delayed electrolyte exhaustion, faster electrophoretic run-speed, and sharper separation of DNA bands from 100 bp to 12 kb in a single run.

  12. Expression, purification, cocrystallization and preliminary crystallographic analysis of sucrose octasulfate/human complement regulator factor H SCRs 6–8

    Energy Technology Data Exchange (ETDEWEB)

    Prosser, Beverly E.; Johnson, Steven; Roversi, Pietro [The Sir William Dunn School of Pathology, The University of Oxford, South Parks Road, Oxford OX1 3RE (United Kingdom); Clark, Simon J. [Faculty of Life Sciences, Manchester University, Michael Smith Building, Oxford Road, Manchester M13 9PT (United Kingdom); Tarelli, Edward [Medical Biomics Centre, St George’s, University of London, Cranmer Terrace, London SW17 0RE (United Kingdom); Sim, Robert B. [The MRC Immunochemistry Unit, The University of Oxford, South Parks Road, Oxford OX1 3RE (United Kingdom); Day, Antony J. [Faculty of Life Sciences, Manchester University, Michael Smith Building, Oxford Road, Manchester M13 9PT (United Kingdom); Lea, Susan M., E-mail: susan.lea@bnc.ox.ac.uk [The Sir William Dunn School of Pathology, The University of Oxford, South Parks Road, Oxford OX1 3RE (United Kingdom)

    2007-06-01

    The crystallization of human complement regulator FH-678{sub 402H} with a glycosaminoglycan analogue is described. Human plasma protein complement factor H (FH) is an inhibitor of the spontaneously activated alternative complement pathway. An allotypic variant of FH, 402His, has been associated with age-related macular degeneration, the leading cause of blindness in the elderly. Crystals of FH domains 6–8 (FH678) containing 402His have been grown in the presence of a polyanionic sucrose octasulfate ligand (an analogue of the natural glycosaminoglycan ligands of FH) using both native and selenomethionine-derivatized protein. Native data sets diffracting to 2.3 Å and SeMet data sets of up to 2.8 Å resolution have been collected. An anomalous difference Patterson map reveals self- and cross-peaks from two incorporated Se atoms. The corresponding selenium substructure has been solved.

  13. Copper Selenidophosphates Cu4P2Se6, Cu4P3Se4, Cu4P4Se3, and CuP2Se, Featuring Zero-, One-, and Two-Dimensional Anions.

    Science.gov (United States)

    Kuhn, Alexander; Schoop, Leslie M; Eger, Roland; Moudrakovski, Igor; Schwarzmüller, Stefan; Duppel, Viola; Kremer, Reinhard K; Oeckler, Oliver; Lotsch, Bettina V

    2016-08-15

    Five new compounds in the Cu/P/Se phase diagram have been synthesized, and their crystal structures have been determined. The crystal structures of these compounds comprise four previously unreported zero-, one-, and two-dimensional selenidophosphate anions containing low-valent phosphorus. In addition to two new modifications of Cu4P2Se6 featuring the well-known hexaselenidohypodiphosphate(IV) ion, there are three copper selenidophosphates with low-valent P: Cu4P3Se4 contains two different new anions, (i) a monomeric (zero-dimensional) selenidophosphate anion [P2Se4](4-) and (ii) a one-dimensional selenidophosphate anion [Formula: see text], which is related to the well-known gray-Se-like [Formula: see text] Zintl anion. Cu4P4Se3 contains one-dimensional [Formula: see text] polyanions, whereas CuP2Se contains the 2D selenidophosphate [Formula: see text] polyanion. It consists of charge-neutral CuP2Se layers separated by a van der Waals gap which is very rare for a Zintl-type phase. Hence, besides black P, CuP2Se constitutes a new possible source of 2D oxidized phosphorus containing layers for intercalation or exfoliation experiments. Additionally, the electronic structures and some fundamental physical properties of the new compounds are reported. All compounds are semiconducting with indirect band gaps of the orders of around 1 eV. The phases reported here add to the structural diversity of chalcogenido phosphates. The structural variety of this family of compounds may translate into a variety of tunable physical properties.

  14. Effects of heparin on insulin binding and biological activity

    International Nuclear Information System (INIS)

    Kriauciunas, K.M.; Grigorescu, F.; Kahn, C.R.

    1987-01-01

    The effect of heparin, a polyanionic glycosaminoglycan known to alter the function of many proteins, on insulin binding and bioactivity was studied. Cultured human lymphocytes (IM-9) were incubated with varying concentrations of heparin, then extensively washed, and 125 I-labeled insulin binding was measured. Heparin at concentrations used clinically for anticoagulation (1-50 U/ml) inhibited binding in a dose-dependent manner; 50% inhibition of binding occurred with 5-10 U/ml. Scatchard analysis indicated that the decrease in binding was due to a decrease in both the affinity and the apparent number of available insulin receptors. The effect occurred within 10 min at 22 degrees C and persisted even after the cells were extensively washed. Inhibition of insulin binding also occurred when cells were preincubated with heparinized plasma or heparinized serum but not when cells were incubated with normal serum or plasma from blood anticoagulated with EDTA. By contrast, other polyanions and polycations, e.g., poly-L-glutamic acid, poly-L-lysine, succinylated poly-L-lysine, and histone, did not inhibit binding. Heparin also inhibited insulin binding in Epstein-Barr (EB) virus-transformed lymphocytes but had no effect on insulin binding to isolated adipocytes, human erythrocytes, or intact hepatoma cells. When isolated adipocytes were incubated with heparin, there was a dose-dependent inhibition of insulin-stimulated glucose oxidation and, to a lesser extent, of basal glucose oxidation. Although heparin has no effect on insulin binding to intact hepatoma cells, heparin inhibited both insulin binding and insulin-stimulated autophosphorylation in receptors solubilized from these cells

  15. Heparin-mimicking multilayer coating on polymeric membrane via LbL assembly of cyclodextrin-based supramolecules.

    Science.gov (United States)

    Deng, Jie; Liu, Xinyue; Ma, Lang; Cheng, Chong; Shi, Wenbin; Nie, Chuanxiong; Zhao, Changsheng

    2014-12-10

    In this study, multifunctional and heparin-mimicking star-shaped supramolecules-deposited 3D porous multilayer films with improved biocompatibility were fabricated via a layer-by-layer (LbL) self-assembly method on polymeric membrane substrates. Star-shaped heparin-mimicking polyanions (including poly(styrenesulfonate-co-sodium acrylate; Star-PSS-AANa) and poly(styrenesulfonate-co-poly(ethylene glycol)methyl ether methacrylate; Star-PSS-EGMA)) and polycations (poly(methyl chloride-quaternized 2-(dimethylamino)ethyl methacrylate; Star-PMeDMA) were first synthesized by atom transfer radical polymerization (ATRP) from β-cyclodextrin (β-CD) based cores. Then assembly of 3D porous multilayers onto polymeric membrane surfaces was carried out by alternating deposition of the polyanions and polycations via electrostatic interaction. The surface morphology and composition, water contact angle, blood activation, and thrombotic potential as well as cell viability for the coated heparin-mimicking films were systematically investigated. The results of surface ATR-FTIR spectra and XPS spectra verified successful deposition of the star-shaped supramolecules onto the biomedical membrane surfaces; scanning electron microscopy (SEM) and atomic force microscopy (AFM) observations revealed that the modified substrate had 3D porous surface morphology, which might have a great biological influence on the biointerface. Furthermore, systematic in vitro investigation of protein adsorption, platelet adhesion, human platelet factor 4 (PF4, indicates platelet activation), activate partial thromboplastin time (APTT), thrombin time (TT), coagulation activation (thrombin-antithrombin III complex (TAT, indicates blood coagulant)), and blood-related complement activation (C3a and C5a, indicates inflammation potential) confirmed that the heparin-mimicking multilayer coated membranes exhibited ultralow blood component activations and excellent hemocompatibility. Meanwhile, after surface coating

  16. Histones bundle F-actin filaments and affect actin structure.

    Directory of Open Access Journals (Sweden)

    Edna Blotnick

    Full Text Available Histones are small polycationic proteins complexed with DNA located in the cell nucleus. Upon apoptosis they are secreted from the cells and react with extracellular polyanionic compounds. Actin which is a polyanionic protein, is also secreted from necrotic cells and interacts with histones. We showed that both histone mixture (histone type III and the recombinant H2A histone bundles F-actin, increases the viscosity of the F-actin containing solution and polymerizes G-actin. The histone-actin bundles are relatively insensitive to increase of ionic strength, unlike other polycation, histatin, lysozyme, spermine and LL-37 induced F-actin bundles. The histone-actin bundles dissociate completely only in the presence of 300-400 mM NaCl. DNA, which competes with F-actin for histones, disassembles histone induced actin bundles. DNase1, which depolymerizes F- to G-actin, actively unbundles the H2A histone induced but slightly affects the histone mixture induced actin bundles. Cofilin decreases the amount of F-actin sedimented by low speed centrifugation, increases light scattering and viscosity of F-actin-histone mixture containing solutions and forms star like superstructures by copolymerizing G-actin with H2A histone. The results indicate that histones are tightly attached to F-actin by strong electrostatic and hydrophobic forces. Since both histones and F-actin are present in the sputum of patients with cystic fibrosis, therefore, the formation of the stable histone-actin bundles can contribute to the pathology of this disease by increasing the viscosity of the sputum. The actin-histone interaction in the nucleus might affect gene expression.

  17. A further extension of pnictide oxide chemistry - synthesis and structure of La{sub 2}AuP{sub 2}O

    Energy Technology Data Exchange (ETDEWEB)

    Eul, Matthias; Moeller, Manfred H.; Hoffmann, Rolf-Dieter; Jeitschko, Wolfgang; Poettgen, Rainer [Institut fuer Anorganische und Analytische Chemie, Universitaet Muenster (Germany)

    2012-02-15

    The phosphide oxide La{sub 2}AuP{sub 2}O was synthesized from lanthanum filings, dried La{sub 2}O{sub 3}, gold pieces, and ground red phosphorus in the ideal 1.33:0.33:1:2 ratio in an evacuated silica tube at 1473 K. Small single crystals were obtained by recrystallization in a NaCl/KCl flux. The structure was determined on the basis of single-crystal X-ray diffractometer data: new type, C2/m, a = 1537.3(3), b = 427.39(8), c = 1009.2(2) pm, β = 131.02(1) , wR{sub 2} = 0.046, 1102 F{sup 2} values, 38 variables. La{sub 2}AuP{sub 2}O contains two striking structural motifs: The oxygen atoms are located in La{sub 4} tetrahedra. The latter are cis-edge-shared forming polymeric cationic [La{sub 2}O]{sup 4+} chains. These cationic units are separated and charge-balanced by [AuP{sub 2}]{sup 4-} polyanions which have monovalent gold in distorted trigonal planar phosphorus coordination. Two crystallographically independent phosphorus sites occur in the polyanion, i.e. isolated P{sup 3-} besides dumb-bells P{sub 2}{sup 4-} (P2-P2 223 pm). La{sub 2}AuP{sub 2}O, which crystallizes in the form of ruby red transparent crystals, is an electron precise phosphide oxide (4La{sup 3+})(2Au{sup +})(2P{sup 3-})(P{sub 2}{sup 4-})(2O{sup 2-}). (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  18. Octakis(dimethyl sulfoxide-κOcerium(III μ6-oxido-dodeca-μ2-oxido-hexaoxidohexamolybdate(VI dimethyl sulfoxide tetrasolvate

    Directory of Open Access Journals (Sweden)

    Arbia Ben Khélifa

    2012-07-01

    Full Text Available The title complex, [Ce(C2H6OS8]2[Mo6O19]3·4C2H6OS, was obtained as a byproduct of the reaction of [(C4H94N]2[Mo6O19] with Ce(NO33·6H2O and phthalic acid in dimethylsulfoxide solution. The asymmetric unit consists of a complex [Ce(C2H6OS8]3+ cation, one and a half of the Lindqvist-type [Mo6O19]2− polyanions and two dimethylsulfoxide solvent molecules; the half polyanion lies on an inversion center. The Ce3+ ion is coordinated by eight dimethylsulfoxide ligands through the O atoms in the form of a distorted square antiprism. The Ce—O bond lengths range from 2.429 (6 to 2.550 (5 Å. The cohesion of the structure is ensured by S...O [3.115 (6, 3.242 (10 and 3.12 (3 Å], O...O [3.037 (10 Å] and C—H...O interactions between cations and anions. The S and C atoms of a dmso ligand are disordered over three sites in a 0.45:0.30:0.25 ratio. The dimethylsulfoxide solvent molecules are highly disordered and could not be modelled successfully; their contribution was therefore removed from the refinement using the SQUEEZE routine in PLATON [Spek (2009. Acta Cryst. D65, 148–155]. Potential solvent-accessible voids of 500.0 Å3 occur in the crystal structure.

  19. Glycosaminoglycan sulphation affects the seeded misfolding of a mutant prion protein.

    Directory of Open Access Journals (Sweden)

    Victoria A Lawson

    Full Text Available BACKGROUND: The accumulation of protease resistant conformers of the prion protein (PrP(res is a key pathological feature of prion diseases. Polyanions, including RNA and glycosaminoglycans have been identified as factors that contribute to the propagation, transmission and pathogenesis of prion disease. Recent studies have suggested that the contribution of these cofactors to prion propagation may be species specific. METHODOLOGY/PRINCIPAL FINDING: In this study a cell-free assay was used to investigate the molecular basis of polyanion stimulated PrP(res formation using brain tissue or cell line derived murine PrP. Enzymatic depletion of endogenous nucleic acids or heparan sulphate (HS from the PrP(C substrate was found to specifically prevent PrP(res formation seeded by mouse derived PrP(Sc. Modification of the negative charge afforded by the sulphation of glycosaminoglycans increased the ability of a familial PrP mutant to act as a substrate for PrP(res formation, while having no effect on PrP(res formed by wildtype PrP. This difference may be due to the observed differences in the binding of wild type and mutant PrP for glycosaminoglycans. CONCLUSIONS/SIGNIFICANCE: Cofactor requirements for PrP(res formation are host species and prion strain specific and affected by disease associated mutations of the prion protein. This may explain both species and strain dependent propagation characteristics and provide insights into the underlying mechanisms of familial prion disease. It further highlights the challenge of designing effective therapeutics against a disease which effects a range of mammalian species, caused by range of aetiologies and prion strains.

  20. Unravelling Local Atomic Order of the Anionic Sublattice in M(Al1-x Gax )4 with M=Sr and Ba by Using NMR Spectroscopy and Quantum Mechanical Modelling.

    Science.gov (United States)

    Pecher, Oliver; Mausolf, Bernhard; Peters, Volker; Lamberts, Kevin; Korthaus, Alexander; Haarmann, Frank

    2016-12-05

    The quasibinary section of the intermetallic phases MAl 4 and MGa 4 with M=Sr and Ba have been characterised by means of X-ray diffraction (XRD) studies and differential thermal analysis. The binary phases show complete miscibility and form solid solutions M(Al 1-x Ga x ) 4 with M=Sr and Ba. These structures crystallise in the BaAl 4 structure type with four- and five-bonded Al and/or Ga atoms (denoted as Al(4b), Al(5b), Ga(4b), and Ga(5b), respectively) that form a polyanionic Al/Ga sublattice. Solid state 27 Al NMR spectroscopic analysis and quantum mechanical (QM) calculations were applied to study the bonding of the Al centres and the influence of Al/Ga substitution, especially in the regimes with low degrees of substitution. M(Al 1-x Ga x ) 4 with M=Sr and Ba and 0.925≤x≤0.975 can be described as a matrix of the binary majority compound in which a low amount of the Ga atoms has been substituted by Al atoms. In good agreement with the QM calculations, 27 Al NMR investigations and single crystal XRD studies prove a preferred occupancy of Al(4b) for these substitution regimes. Furthermore, two different local Al environments were found, namely isolated Al(4b1) atoms and Al(4b2), due to the formation of Al(4b)-Al(4b) pairs besides isolated Al(4b) atoms within the polyanionic sublattice. QM calculations of the electric field gradient (EFG) using superlattice structures under periodic boundary conditions are in good agreement with the NMR spectroscopic results. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Tuning smart microgel swelling and responsive behavior through strong and weak polyelectrolyte pair assembly.

    Science.gov (United States)

    Costa, Eunice; Lloyd, Margaret M; Chopko, Caroline; Aguiar-Ricardo, Ana; Hammond, Paula T

    2012-07-03

    The layer-by-layer (LbL) assembly of polyelectrolyte pairs on temperature and pH-sensitive cross-linked poly(N-isopropylacrylamide)-co-(methacrylic acid), poly(NIPAAm-co-MAA), microgels enabled a fine-tuning of the gel swelling and responsive behavior according to the mobility of the assembled polyelectrolyte (PE) pair and the composition of the outermost layer. Microbeads with well-defined morphology were initially prepared by synthesis in supercritical carbon dioxide. Upon LbL assembly of polyelectrolytes, interactions between the multilayers and the soft porous microgel led to differences in swelling and thermoresponsive behavior. For the weak PE pairs, namely poly(L-lysine)/poly(L-glutamic acid) and poly(allylamine hydrochloride)/poly(acrylic acid), polycation-terminated microgels were less swollen and more thermoresponsive than native microgel, whereas polyanion-terminated microgels were more swollen and not significantly responsive to temperature, in a quasi-reversible process with consecutive PE assembly. For the strong PE pair, poly(diallyldimethylammonium chloride)/poly(sodium styrene sulfonate), the differences among polycation and polyanion-terminated microgels are not sustained after the first PE bilayer due to extensive ionic cross-linking between the polyelectrolytes. The tendencies across the explored systems became less noteworthy in solutions with larger ionic strength due to overall charge shielding of the polyelectrolytes and microgel. ATR FT-IR studies correlated the swelling and responsive behavior after LbL assembly on the microgels with the extent of H-bonding and alternating charge distribution within the gel. Thus, the proposed LbL strategy may be a simple and flexible way to engineer smart microgels in terms of size, surface chemistry, overall charge and permeability.

  2. Quantum mechanical design of efficient second-order nonlinear optical materials based on heteroaromatic imido-substituted hexamolybdates: first theoretical framework of POM-based heterocyclic aromatic rings.

    Science.gov (United States)

    Janjua, Muhammad Ramzan Saeed Ashraf

    2012-11-05

    This work was inspired by a previous report (Janjua et al. J. Phys. Chem. A 2009, 113, 3576-3587) in which the nonlinear-optical (NLO) response strikingly improved with an increase in the conjugation path of the ligand and the nature of hexamolybdates (polyoxometalates, POMs) was changed into a donor by altering the direction of charge transfer with a second aromatic ring. Herein, the first theoretical framework of POM-based heteroaromatic rings is found to be another class of excellent NLO materials having double heteroaromatic rings. First hyperpolarizabilities of a large number of push-pull-substituted conjugated systems with heteroaromatic rings have been calculated. The β components were computed at the density functional theory (DFT) level (BP86 geometry optimizations and LB94 time-dependent DFT). The largest β values are obtained with a donor (hexamolybdates) on the benzene ring and an acceptor (-NO(2)) on pyrrole, thiophene, and furan rings. The pyrrole imido-substituted hexamolybdate (system 1c) has a considerably large first hyperpolarizability, 339.00 × 10(-30) esu, and it is larger than that of (arylimido)hexamolybdate, calculated as 0.302 × 10(-30) esu (reference system 1), because of the double aromatic rings in the heteroaromatic imido-substituted hexamolybdates. The heteroaromatic rings act as a conjugation bridge between the electron acceptor (-NO(2)) and donor (polyanion). The introduction of an electron donor into heteroaromatic rings significantly enhances the first hyperpolarizabilities because the electron-donating ability is substantially enhanced when the electron donor is attached to the heterocyclic aromatic rings. Interposing five-membered auxiliary fragments between strong donor (polyanion) or acceptor (-NO(2)) groups results in a large computed second-order NLO response. The present investigation provides important insight into the NLO properties of (heteroaromatic) imido-substituted hexamolybdate derivatives because these compounds

  3. Polyethylenedioxythiophene and molybdenum disulfide nanocomposite electrodes for supercapacitor applications

    International Nuclear Information System (INIS)

    Alamro, Turki; Ram, Manoj K.

    2017-01-01

    Highlights: • MoS_2-PEDOT nanocomposite electrode material was synthesized using polyanion ‘PSS’ and surfactant CTAB in an aqueous media. • The supercapacitor based on composite MoS_2-PEDOT electrode revealed higher energy density than graphene composite electrodes. • The specific capacitance of 361 Farad/gram (F/g) was obtained for 1:2 weight ratio of MoS2 to the EDOT monomer in MoS_2-PEDOT nanocomposite based electrodes. - Abstract: An innovative nanocomposite electrode was chemically synthesized using molybdenum disulphide (MoS_2)- polyethylenedioxythiophene (PEDOT) to understand the charge mechanism in a symmetric supercapacitor. The MoS_2-PEDOT nanocomposite was produced at various ratios of MoS_2 to ethylenedioxythiophene (EDOT) in an aqueous medium of polyanions polystyrene sulfonate (PSS) and cetyltrimethylammonium bromide (CTAB) at controlled conditions. The morphology, crystallinity, and optical properties of MoS_2-PEDOT nanocomposite materials were characterized using scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, particle size analyzer, Raman spectroscopy, X-ray-diffraction, and transmission electron microscopy (TEM) techniques, respectively. The electrochemical properties of the supercapacitor were investigated using cyclic voltammetry, charging–discharging at constant current and electrochemical impedance spectroscopy (EIS) techniques. The specific capacitance, power and energy densities of the supercapacitor were estimated using cyclic voltammetry (CV), charging–discharging, Nyquist and Bode plots. The specific capacitance was estimated to be 361 Farad/gram (F/g) for the 1:2 weight ratio of MoS_2 to the EDOT monomer in the MoS_2-PEDOT nanocomposite based electrodes. Nevertheless, this study provides a fundamental aspect of synthesis of nanocomposite material for optimum attainment supercapacitive properties based on the MoS_2-PEDOT nanocomposite electrode for practical energy storage applications.

  4. Magnesium and cadmium in covalently-bonded Lonsdaleite networks: Synthesis, structure, and conding of AETMg{sub 2} and SrTCd{sub 2} (AE = Ca, Sr; T = Pd, Ag, Pt, Au)

    Energy Technology Data Exchange (ETDEWEB)

    Kersting, Marcel; Johnscher, Michael; Poettgen, Rainer [Institut fuer Anorganische und Analytische Chemie, Universitaet Muenster, Corrensstrasse 30, 48149 Muenster (Germany); Matar, Samir F. [Universite Bordeaux, ICMCB, UPR 9048, 33600 Pessac (France)

    2013-04-15

    The alkaline earth metal compounds AETMg{sub 2} and AETCd{sub 2} (AE = Ca, Sr; T = Pd, Ag, Pt, Au) were synthesized by induction-melting (or in muffle furnaces) of the elements in sealed niobium ampoules. The new phases were characterized by powder X-ray diffraction. The structures of SrPdMg{sub 2} and SrPdCd{sub 2} were investigated by X-ray diffraction on single crystals: MgCuAl{sub 2} type, Cmcm, a = 436.42(4), b = 1130.1(1), c = 820.54(7) pm, wR{sub 2} = 0.0115, 511 F{sup 2} values for SrPdMg{sub 2} and a = 443.5(2), b = 1063.0(2), c = 810.2(2) pm, wR{sub 2} = 0.0296, 386 F{sup 2} values for SrPdCd{sub 2} with 16 variables for each refinement. The magnesium and cadmium atoms build up [TMg{sub 2}] and [TCd{sub 2}] polyanionic networks, which leave cavities for the calcium and strontium atoms. The bonding variations within the polyanions, which are mainly influenced by the length of the b axis are discussed. Ab initio calculations of electronic structure, charge densities, and chemical bonding, characterize SrPdMg{sub 2} with a larger cohesive energy than SrPdCd{sub 2}. This is illustrated by larger bonding Pd-Mg interactions, opposite to compensating Pd-Cd between bonding and antibonding states. (Copyright copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  5. Europium(II)heptaphosphide EuP/sub 7/

    Energy Technology Data Exchange (ETDEWEB)

    von Schnering, H G; Wittmann, M

    1980-07-01

    The novel polyphosphide, EuP/sub 7/, was prepared under controlled conditions by reaction of the elements in salt melts at 750-800 K. EuP/sub 7/ forms black prismatic crystals not attacked by dilute mineral acids and bases. The thermal decomposition yields EuP/sub 3/ at 700 K and in further steps EuP/sub 2/, Eu/sub 3/P/sub 4/ and EuP, respectively. According to the crystal structure as well as the electrical, optical and magnetic properties, EuP/sub 7/ is a semiconductor (Esub(G) = 0.9 eV; Esub(G) (vert) = 1.1 eV) with divalent europium (..mu.. = 7.55 B.M.). The compound crystallizes in the monoclinic space group P 2/sub 1//n with a = 1148.8(7) pm, b = 570.0(3) pm, c = 1061.0(6) pm, and ..beta.. = 106.08/sup 0/(5); (X-ray diffraction data; 1479 hkl; R = 0.031). The P-atoms are connected ((P-P) = 218.0-223.5 pm) to a 2-dimensional infinite polyanionic structure 2sub(infinity)(P/sub 7//sup 2 -/) with homonuclear 3-bonded and 2-bonded P-atoms in the ratio 5 : 2. The polyanionic network contains P/sub 6/-rings (chair conformation) as well as P/sub 8/-rings and P/sub 10/-rings. The Eu-atoms are bonded to 9 P-atoms (1,4,4-polyhedra) with bond distances ranging from 306.6 to 326.6 pm. The Eu-atoms complete the tetrahedral environment of the P-atoms.

  6. Controllable synthesis, crystal structure and magnetic properties of Monomer-Dimer Cocrystallized MnIII Salen-type composite material

    Science.gov (United States)

    Wu, Qiong; Wu, Wei; Wu, Yongmei; Li, Weili; Qiao, Yongfeng; Wang, Ying; Wang, Baoling

    2018-04-01

    By the reaction of manganese-Schiff-base complexes with penta-anionic Anderson heteropolyanion, a new supramolecular architecture [Mn2(Salen)2(H2O)2][Mn(Salen)(H2O)2]2Na[IMo6O24]·8H2O (1) (salen = N,N‧-ethylene-bis (salicylideneiminate) has been isolated. Compound 1 was characterized by the single-crystal X-ray diffraction, elemental, IR and thermal gravimetric analyses. Structural analysis reveals that the unit cell simultaneously contains MnIII-Salen dimer and monomer cation fragments, for which the Anderson-type polyanions serve as counter anions. In the packing arrangement, all the MnIII dimers are well separated by polyoxometalate units and form tertiary structure together with MnIII monomers. Interestingly, different from the previous work, in the exact same reaction conditions, we are able to template MnIII-Salen complexes into different configurations by varying the charge state of polyanions. Besides, the magnetic properties of 1 were also examined by using both dc and ac magnetic field of the superconducting quantum interference devices. Most importantly, our fitting of the experimental data to a Heisenberg-type spin model shows that there exists a ferromagnetic exchange interaction ∼5 K between the spins (S = 2) on MnIII in the dimer, while antiferromagnetic ones exist among monomers and dimer (∼2 K). This meta-magnetic state could induce a slight spin frustration at low temperature, which would in turn affect the magnetic behavior. In addition, our ac field measurement of the susceptibilities suggests a typical signature for a single-molecule magnet.

  7. Proton and metal ion binding to natural organic polyelectrolytes-I. Studies with synthetic model compounds

    Science.gov (United States)

    Marinsky, J.A.; Reddy, M.M.

    1984-01-01

    A unified physico-chemical model, based on a modified Henderson-Hasselbalch equation, for the analysis of ion complexation reactions involving charged polymeric systems is presented and verified. In this model pH = pKa+p(??Ka) + log(??/1 - ??) where Ka is the intrinsic acid dissociation constant of the ionizable functional groups on the polymer, ??Ka is the deviation of the intrinsic constant due to electrostatic interaction between the hydrogen ion and the polyanion, and alpha (??) is the polyacid degree of ionization. Using this approach pKa values for repeating acidic units of polyacrylic (PAA) and polymethacrylic (PMA) acids were found to be 4.25 ?? 0.03 and 4.8 ?? 0.1, respectively. The polyion electrostatic deviation term derived from the potentiometric titration data (i.e. p(??Ka)) is used to calculate metal ion concentration at the complexation site on the surface of the polyanion. Intrinsic cobalt-polycarboxylate binding constants (7.5 for PAA and 5.6 for PMA), obtained using this procedure, are consistent with the range of published binding constants for cobalt-monomer carboxylate complexes. In two phase systems incorporation of a Donnan membrane potential term allows determination of the intrinsic pKa of a cross-linked PMA gel, pKa = 4.83, in excellent agreement with the value obtained for the linear polyelectrolyte and the monomer. Similarly, the intrinsic stability constant for cobalt ion binding to a PMA-gel (??CoPMA+ = 11) was found to be in agreement with the linear polyelectrolyte analogue and the published data for cobalt-carboxylate monodentate complexes. ?? 1984.

  8. Histones bundle F-actin filaments and affect actin structure.

    Science.gov (United States)

    Blotnick, Edna; Sol, Asaf; Muhlrad, Andras

    2017-01-01

    Histones are small polycationic proteins complexed with DNA located in the cell nucleus. Upon apoptosis they are secreted from the cells and react with extracellular polyanionic compounds. Actin which is a polyanionic protein, is also secreted from necrotic cells and interacts with histones. We showed that both histone mixture (histone type III) and the recombinant H2A histone bundles F-actin, increases the viscosity of the F-actin containing solution and polymerizes G-actin. The histone-actin bundles are relatively insensitive to increase of ionic strength, unlike other polycation, histatin, lysozyme, spermine and LL-37 induced F-actin bundles. The histone-actin bundles dissociate completely only in the presence of 300-400 mM NaCl. DNA, which competes with F-actin for histones, disassembles histone induced actin bundles. DNase1, which depolymerizes F- to G-actin, actively unbundles the H2A histone induced but slightly affects the histone mixture induced actin bundles. Cofilin decreases the amount of F-actin sedimented by low speed centrifugation, increases light scattering and viscosity of F-actin-histone mixture containing solutions and forms star like superstructures by copolymerizing G-actin with H2A histone. The results indicate that histones are tightly attached to F-actin by strong electrostatic and hydrophobic forces. Since both histones and F-actin are present in the sputum of patients with cystic fibrosis, therefore, the formation of the stable histone-actin bundles can contribute to the pathology of this disease by increasing the viscosity of the sputum. The actin-histone interaction in the nucleus might affect gene expression.

  9. Copper in soil fractions and runoff in a vineyard catchment: Insights from copper stable isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Babcsányi, Izabella; Chabaux, François; Granet, Mathieu; Meite, Fatima; Payraudeau, Sylvain; Duplay, Joëlle; Imfeld, Gwenaël, E-mail: imfeld@unistra.fr

    2016-07-01

    Understanding the fate of copper (Cu) fungicides in vineyard soils and catchments is a prerequisite to limit the off-site impact of Cu. Using Cu stable isotopes, Cu retention in soils and runoff transport was investigated in relation to the use of Cu fungicides and the hydrological conditions in a vineyard catchment (Rouffach, Haut-Rhin, France; mean slope: 15%). The δ{sup 65}Cu values of the bulk vineyard soil varied moderately through the depth of the soil profiles (− 0.12 to 0.24‰ ± 0.08‰). The values were in the range of those of the fungicides (− 0.21 to 0.11‰) and included the geogenic δ{sup 65}Cu value of the untreated soil (0.08‰). However, δ{sup 65}Cu values significantly differed between particle-size soil fractions (− 0.37 ± 0.10‰ in fine clays and 0.23 ± 0.07‰ in silt). Together with the soil mineralogy, the results suggested Cu isotope fractionation primarily associated with the clay and fine clay fractions that include both SOM and mineral phases. The vegetation did not affect the Cu isotope patterns in the vineyard soils. Cu export by runoff from the catchment accounted for 1% of the applied Cu mass from 11th May to 20{sup th} July 2011, covering most of the Cu use period. 84% of the exported Cu mass was Cu bound to suspended particulate matter (SPM). The runoff displayed δ{sup 65}Cu values from 0.52 to 1.35‰ in the dissolved phase (< 0.45 μm) compared to − 0.34 to − 0.02‰ in the SPM phase, indicating that clay and fine clay fractions were the main vectors of SPM-bound Cu in runoff. Overall, this study shows that Cu stable isotopes may allow identifying the Cu distribution in the soil fractions and their contribution to Cu export in runoff from Cu-contaminated catchments. - Highlights: • We investigated Cu sorption processes in vineyard soils and runoff transport. • Cu export by runoff from the catchment accounted for 1% of the applied Cu mass. • δ{sup 65}Cu values differed between the particle-size soil

  10. Copper in soil fractions and runoff in a vineyard catchment: Insights from copper stable isotopes

    International Nuclear Information System (INIS)

    Babcsányi, Izabella; Chabaux, François; Granet, Mathieu; Meite, Fatima; Payraudeau, Sylvain; Duplay, Joëlle; Imfeld, Gwenaël

    2016-01-01

    Understanding the fate of copper (Cu) fungicides in vineyard soils and catchments is a prerequisite to limit the off-site impact of Cu. Using Cu stable isotopes, Cu retention in soils and runoff transport was investigated in relation to the use of Cu fungicides and the hydrological conditions in a vineyard catchment (Rouffach, Haut-Rhin, France; mean slope: 15%). The δ"6"5Cu values of the bulk vineyard soil varied moderately through the depth of the soil profiles (− 0.12 to 0.24‰ ± 0.08‰). The values were in the range of those of the fungicides (− 0.21 to 0.11‰) and included the geogenic δ"6"5Cu value of the untreated soil (0.08‰). However, δ"6"5Cu values significantly differed between particle-size soil fractions (− 0.37 ± 0.10‰ in fine clays and 0.23 ± 0.07‰ in silt). Together with the soil mineralogy, the results suggested Cu isotope fractionation primarily associated with the clay and fine clay fractions that include both SOM and mineral phases. The vegetation did not affect the Cu isotope patterns in the vineyard soils. Cu export by runoff from the catchment accounted for 1% of the applied Cu mass from 11th May to 20"t"h July 2011, covering most of the Cu use period. 84% of the exported Cu mass was Cu bound to suspended particulate matter (SPM). The runoff displayed δ"6"5Cu values from 0.52 to 1.35‰ in the dissolved phase (< 0.45 μm) compared to − 0.34 to − 0.02‰ in the SPM phase, indicating that clay and fine clay fractions were the main vectors of SPM-bound Cu in runoff. Overall, this study shows that Cu stable isotopes may allow identifying the Cu distribution in the soil fractions and their contribution to Cu export in runoff from Cu-contaminated catchments. - Highlights: • We investigated Cu sorption processes in vineyard soils and runoff transport. • Cu export by runoff from the catchment accounted for 1% of the applied Cu mass. • δ"6"5Cu values differed between the particle-size soil fractions. • The clay soil

  11. Parcours d’un roman postcolonial francophone en France et en Allemagne : Le Cœur des enfants léopards, de Wilfried N’Sondé

    Directory of Open Access Journals (Sweden)

    Myriam Louviot

    2010-12-01

    Full Text Available En 2007, Wilfried N’Sondé, Franco-congolais vivant à Berlin, publie en France son premier roman, Le Cœur des enfants léopards. Le livre rencontre un certain succès. Un an plus tard, la traduction allemande, Das Herz der Leopardenkinder semble faire une carrière comparable en Allemagne. On serait donc tenté de conclure qu’il n’y a pas tant de différence entre le lectorat français et le lectorat allemand. Un bon roman est un bon roman et il semble normal qu’il trouve son public des deux côtés du Rhin... Mais à y regarder de plus près, il apparaît que la réception du roman de Wilfried N’Sondé en France et en Allemagne suit des voies bien différentes. En France, les littératures postcoloniales sont essentiellement considérées à l’intérieur du cadre conceptuel de la francophonie et le roman de N’Sondé apparaît effectivement d’abord comme un roman francophone ; en Allemagne, il est plutôt rattaché à la littérature de la migration et est compris en fonction des traditions d’analyse qui s’y rattachent.2007 veröffentlicht der in Berlin lebende und aus Kongo stammende Franzose Wilfried N’Sondé, seinen ersten Roman, Le cœur des enfants léopards. Das Buch erfreut sich in Frankreich einer regen Aufmerksamkeit. Ein Jahr später scheint die deutsche Übersetzung, Das Herz der Leopardenkinder, am französischen Erfolg anzuknüpfen : ein guter Roman bleibt ein guter Roman und so scheint es nur normal dass, er auf beiden Seiten des Rheins sein Publikum findet. Dennoch wäre es falsch, daraus auf eine sehr ähnliche Leserschaft in den beiden Sprachräumen zu schließen. Bei genauerem Hinsehen zeigt sich, dass die Rezeption von Wilfried N’Sondés Roman in Frankreich und in Deutschland sehr unterschiedlich verläuft. Während der Roman in Frankreich im Kontext der postkolonialen Literatur in erster Linie als frankophones Werk rezipiert wird, konzentriert sich die deutsche Rezeption vornehmlich auf den

  12. Sedimentary uranium deposits in France and French Union; Les gisements uraniferes dans les formations sedimentaires en France et dans l'Union francaise

    Energy Technology Data Exchange (ETDEWEB)

    Kervella, F [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1958-07-01

    The author gives the actual state of our knowledge on uranium deposits found in recent years. Till now in precambrian formations only one important deposit has been found, at Mounana (Gabon) in a series of conglomeratic sandstones belonging to the 'Francevillien'. The observed mineralization is of the uranium-vanadium type. To the carboniferous formations corresponds in France a series of deposits, among which the most important ones are located at Saint-Hippolyte. Uranium as carburans, organic-bound complexes, is contained in lacustrine schists of Westphalian or lower Stephanian formations. A number of occurrences are also known in permo-triassic formations, particularly in the Vanoise Alps, in the Maritime Alps and in the Herault, where important occurrences have recently been found not far from Lodeve. The cretaceous and tertiary systems contain uranium deposits in phosphate rocks (Morocco, Senegal, Togo, Middle-Congo). Two sedimentary oligocene deposits are known in France. Lastly, the Vinaninkarena deposit in Madagascar, known for a long time, is the only important one reported in the quaternary series. (author) [French] L'auteur fait le point des connaissances acquises sur les gisements decouverts dans les formations sedimentaires en France et dans l'Union francaise au cours des dernieres annees. Les gisements sont classes selon l'age de la formation dans laquelle on les observe. Les terrains precambriens n'ont pour l'instant fourni qu'un seul gisement notable; situe a Mouana (Gabon). C'est en decembre 1956 que cet important gisement fut decouvert dans une serie de gres conglomeratiques appartenant au Francevillien. La mineralisation observee est du type vanadium-uranium. Au carbonifere correspond en France metropolitaine une serie de gisements d'interet variable. Les plus importants sont ceux de Saint-Hippolyte (Haut-Rhin) ou l'uranium est contenu dans des schistes lacustres du Westphalien ou du Stephanien inferieur. L'uranium n'y existe pas sous forme

  13. Atmospheric anthropic impacts tracked by the French atmospheric mobile observatory

    Science.gov (United States)

    Cuesta, J.; Chazette, P.; Flamant, P. H.

    2009-04-01

    A new ATmospheric Mobile ObServatory, so called "ATMOS", has been developed by the LiMAG "Lidar, Meteorology and Geophysics" team of the Institut Pierre Simon Laplace (IPSL) in France, in order to contribute to international field campaigns for studying atmospheric physico-chemistry, air quality and climate (i.e. aerosols, clouds, trace gazes, atmospheric dynamics and energy budget) and the ground-based validation of satellite observations. ATMOS has been deployed in the framework of i) LISAIR, for monitoring air quality in Paris in 2005, ii) AMMA "African Monsoon Multidisciplinary Analysis", in Tamanrasset and in Niamey for observing the aerosols and the atmospheric boundary layer in the Sahara and in the Sahel in 2006, iii) COPS "Convectively and Orographycally driven Precipitation Study" in the Rhin Valley in 2007 and iv) the validation of the spatial mission CALIPSO, launched in April 2006. In the coming years, ATMOS will be deployed i) in the Paris Megacity, in the framework of MEGAPOLI (2009-2010), ii) in southern France (near Marseille) for the Chemistry-Aerosol Mediterranean Experiment CHARMEX (2011-2012) and iii) the validation of ADM-Aeolus in 2010-2011 and Earth-Care in 2012. ATMOS payload is modular, accounting for the different platforms, instruments and measuring techniques. The deployment of ATMOS is an essential contribution to field campaigns, complementing the fixed sites, and a potential alternative of airborne platforms, heavier and more expensive. ATMOS mobile payload comprises both the remote sensing platform MOBILIS ("Moyens mOBIles de téLédetection de l'IPSL") and the in-situ physico-chemical station SAMMO ("Station Aérosols et chiMie MObile"). MOBILIS is an autonomous and high-performance system constituted by a full set of active and passive remote sensing instrumentation (i.e. Lidars and radiometers), whose payload may be adapted for either i) long term fixed monitoring in a maritime container or a shelter, ii) ground-based transect

  14. Architecture of a consent management suite and integration into IHE-based Regional Health Information Networks.

    Science.gov (United States)

    Heinze, Oliver; Birkle, Markus; Köster, Lennart; Bergh, Björn

    2011-10-04

    The University Hospital Heidelberg is implementing a Regional Health Information Network (RHIN) in the Rhine-Neckar-Region in order to establish a shared-care environment, which is based on established Health IT standards and in particular Integrating the Healthcare Enterprise (IHE). Similar to all other Electronic Health Record (EHR) and Personal Health Record (PHR) approaches the chosen Personal Electronic Health Record (PEHR) architecture relies on the patient's consent in order to share documents and medical data with other care delivery organizations, with the additional requirement that the German legislation explicitly demands a patients' opt-in and does not allow opt-out solutions. This creates two issues: firstly the current IHE consent profile does not address this approach properly and secondly none of the employed intra- and inter-institutional information systems, like almost all systems on the market, offers consent management solutions at all. Hence, the objective of our work is to develop and introduce an extensible architecture for creating, managing and querying patient consents in an IHE-based environment. Based on the features offered by the IHE profile Basic Patient Privacy Consent (BPPC) and literature, the functionalities and components to meet the requirements of a centralized opt-in consent management solution compliant with German legislation have been analyzed. Two services have been developed and integrated into the Heidelberg PEHR. The standard-based Consent Management Suite consists of two services. The Consent Management Service is able to receive and store consent documents. It can receive queries concerning a dedicated patient consent, process it and return an answer. It represents a centralized policy enforcement point. The Consent Creator Service allows patients to create their consents electronically. Interfaces to a Master Patient Index (MPI) and a provider index allow to dynamically generate XACML-based policies which are

  15. Structural determination of functional units of the nucleotide binding domain (NBD94 of the reticulocyte binding protein Py235 of Plasmodium yoelii.

    Directory of Open Access Journals (Sweden)

    Ardina Grüber

    2010-02-01

    Full Text Available Invasion of the red blood cells (RBC by the merozoite of malaria parasites involves a large number of receptor ligand interactions. The reticulocyte binding protein homologue family (RH plays an important role in erythrocyte recognition as well as virulence. Recently, it has been shown that members of RH in addition to receptor binding may also have a role as ATP/ADP sensor. A 94 kDa region named Nucleotide-Binding Domain 94 (NBD94 of Plasmodium yoelii YM, representative of the putative nucleotide binding region of RH, has been demonstrated to bind ATP and ADP selectively. Binding of ATP or ADP induced nucleotide-dependent structural changes in the C-terminal hinge-region of NBD94, and directly impacted on the RBC binding ability of RH.In order to find the smallest structural unit, able to bind nucleotides, and its coupling module, the hinge region, three truncated domains of NBD94 have been generated, termed NBD94(444-547, NBD94(566-663 and NBD94(674-793, respectively. Using fluorescence correlation spectroscopy NBD94(444-547 has been identified to form the smallest nucleotide binding segment, sensitive for ATP and ADP, which became inhibited by 4-Chloro-7-nitrobenzofurazan. The shape of NBD94(444-547 in solution was calculated from small-angle X-ray scattering data, revealing an elongated molecule, comprised of two globular domains, connected by a spiral segment of about 73.1 A in length. The high quality of the constructs, forming the hinge-region, NBD94(566-663 and NBD94(674-793 enabled to determine the first crystallographic and solution structure, respectively. The crystal structure of NBD94(566-663 consists of two helices with 97.8 A and 48.6 A in length, linked by a loop. By comparison, the low resolution structure of NBD94(674-793 in solution represents a chair-like shape with three architectural segments.These structures give the first insight into how nucleotide binding impacts on the overall structure of RH and demonstrates the

  16. Solid-state syntheses and single-crystal characterizations of three tetravalent thorium and uranium silicates

    International Nuclear Information System (INIS)

    Jin, Geng Bang; Soderholm, L.

    2015-01-01

    Colorless crystals of ThSiO 4 (huttonite) (1) and (Ca 0.5 Na 0.5 ) 2 NaThSi 8 O 20 (2) have been synthesized by the solid-state reactions of ThO 2 , CaSiO 3 , and Na 2 WO 4 at 1073 K. Green crystals of (Ca 0.5 Na 0.5 ) 2 NaUSi 8 O 20 (3) have been synthesized by the solid-state reactions of UO 2 , CaSiO 3 , and Na 2 WO 4 at 1003 K. All three compounds have been characterized by single-crystal X-ray diffraction. Compound 1 adopts a monazite-type three-dimensional condensed structure, which is built from edge- and corner-shared ThO 9 polyhedra and SiO 4 tetrahedra. Compounds 2 and 3 are isostructural and they crystallize in a steacyite-type structure. The structure consists of discrete pseudocubic [Si 8 O 20 ] 8− polyanions, which are connected by An 4+ cations into a three-dimensional framework. Each An atom coordinates to eight monodentate [Si 8 O 20 ] 8− moieties in a square antiprismatic geometry. Na + and Ca 2+ ions reside in the void within the framework. Raman spectra of 1, 2, and 3 were collected on single crystal samples. 1 displays more complex vibrational bands than thorite. Raman spectra of 2 and 3 are analogous with most of vibrational bands located at almost the same regions. - Graphical abstract: A Raman spectrum and crystal structures of (Ca 0.5 Na 0.5 ) 2 NaAnSi 8 O 20 (An=Th, U), which contain pseudocubic [Si 8 O 20 ] 8− polyanions and eight-coordinate An 4+ cations. - Highlights: • Single crystal growth of three tetravalent actinide silicates from melts. • Single-crystal structures and Raman spectra of (Ca 0.5 Na 0.5 ) 2 NaAnSi 8 O 20 (An=Th, U). • First report of Raman spectrum of huttonite on single crystal samples

  17. The new mixed cluster trielide K{sub 3}Ga{sub 11-x}In{sub x} (x = 1.16-1.36). Synthesis, crystal chemistry, and chemical bonding

    Energy Technology Data Exchange (ETDEWEB)

    Falk, Martha; Meyer, Carolin; Roehr, Caroline [Institut fuer Anorganische und Analytische Chemie, Universitaet Freiburg (Germany)

    2017-12-13

    The new cluster compound K{sub 3}Ga{sub 11-x}In{sub x}, which exhibits a very small In/Ga phase width of x = 1.16 to 1.36 only, was obtained in the course of a systematic synthetic, crystallographic and bond theoretical investigation of mixed potassium trielides of the ternary system K-In-Ga. The compound, which was synthesized from nearly stoichiometric amounts of the elements at a maximum temperature of 500 C, crystallizes in a new orthorhombic crystal structure type [space group Cmmm, a = 1577.9(5), b = 3355.1(8), c = 655.2(2) pm, Z = 10, R{sub 1} = 0.0471]. In the complex polyanion, the triels form two crystallographically different [Ga{sub 12}] icosahedra, which are present in a 1:2 ratio, and a previously unknown [M{sub 13}] ''double-cluster'' consisting of two vertex-sharing [M{sub 7}] pentagonal bipyramids. All clusters are connected among each other and via a four-bonded pure In and Ga atom [In(1), Ga(1)]. The polyanion of the compound with the overall formula K{sub 15}M{sub 55} can thus be split up according to [Ga(1X){sub 12}][Ga(2X){sub 12}]{sub 2}[M(3X){sub 13}]In(1){sub 4}Ga(1){sub 2}. Herein, the all-exo bonded closo icosahedra carry a charge of -2, the six four-bonded In/Ga contribute with a charge of -6 and the new [M{sub 13}] ''double-cluster'' thus carries a charge of -3. Under the reasonable assumption of an ''intermediate'' interaction between the two cluster fragments, this charge, i.e. the presence of 15 skeleton electron pairs, is in accordance with the mno electron counting rules. FP-LAPW DFT band structure calculations of two ordered model compounds support this interpretation: The tDOS exhibits a small bandgap and the electron density map suggests a limited additional interaction between the Ga{sub 5} bases of the two bipyramidal cluster fragments. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  18. Waht is 'molybdic acid' or 'polymolybdic acid'?

    International Nuclear Information System (INIS)

    Tytko, K.H.; Baethe, G.; Mehmke, K.

    1987-01-01

    According to a comparative study of the literature, supplemented by well-aimed experimental investigations and equilibrium calculations, the terms 'molybdic acid' or 'polymolybdic acid', used for many substances, species, or solutions in the literature, are applicable to a species, a solution, and two solids: a) The monomeric molybdic acid, most probably having the formula MoO 2 (OH) 2 (H 2 O) 2 (= H 2 MoO 4 , aq), exists in (aqueous) solution only and never exceeds a concentration of ∼ 10 -3 M since at higher concentrations it reacts with other monomeric molybdenum(VI) species to give anionic or cationic polymers. b) A concentrated (> 0.1 M Mo VI ) aqueous molybdate solution of degree of acidification P = 2 (realized, e.g., by a solution of one of the Mo VI oxides; by any molybdate solutions whose cations have been exchanged by H 2 O + on a cation exchanger; by suitable acidification of a molybdate solution) contains 8 H 3 O + and the well-known polyanion Mo 36 O 112 (H 2 O) 16 8- exactly in the stoichiometric proportions. c) A glassy substance, obtained from an alkali metal salt-free solution prepared acording to (b), refers to the compound (H 3 O) 8 [Mo 36 O 112 (H 2 O) 16 ] · xH 2 O, x = 25 - 29. d) A solid having the ideal composition [(H 3 O)Mo 5 O 15 (OH)H 2 O · H 2 O] ∞ consists of a polymolybdate skeleton (the well-known 'decamolybdate' structure), in the tunnels of which H 3 O + and H 2 O are intercalated. The structure is very unstable if only H 3 O + cations are present, but it is enormously stabilized by a partial exchange of H 3 O + by certain alkali or alkaline earth metal cations. For the compounds MoO 3 , MoO 3 ·H 2 O, and MoO 3 · 2 H 2 O the term 'molybdic acid' is unjustified. The commercial product 'molybdic acid, ∼ 85% MoO 3 ' is the well-known polymolybdate (NH 4 ) 2 O · 4 MoO 3 with a layer structure of the polyanion. 84 refs. (author)

  19. Analysis of Lipoplex Structure and Lipid Phase Changes

    Energy Technology Data Exchange (ETDEWEB)

    Koynova, Rumiana

    2012-07-18

    Efficient delivery of genetic material to cells is needed for tasks of utmost importance in the laboratory and clinic, such as gene transfection and gene silencing. Synthetic cationic lipids can be used as delivery vehicles for nucleic acids and are now considered the most promising nonviral gene carriers. They form complexes (lipoplexes) with the polyanionic nucleic acids. A critical obstacle for clinical application of the lipid-mediated DNA delivery (lipofection) is its unsatisfactory efficiency for many cell types. Understanding the mechanism of lipid-mediated DNA delivery is essential for their successful application, as well as for a rational design and synthesis of novel cationic lipoid compounds for enhanced gene delivery. A viewpoint now emerging is that the critical factor in lipid-mediated transfection is the structural evolution of lipoplexes within the cell, upon interacting and mixing with cellular lipids. In particular, recent studies showed that the phase evolution of lipoplex lipids upon interaction and mixing with membrane lipids appears to be decisive for transfection success: specifically, lamellar lipoplex formulations, which were readily susceptible to undergoing lamellar-nonlamellar phase transition upon mixing with cellular lipids and were found rather consistently associated with superior transfection potency, presumably as a result of facilitated DNA release. Thus, understanding the lipoplex structure and the phase changes upon interacting with membrane lipids is important for the successful application of the cationic lipids as gene carriers.

  20. Construction of covalently attached enzyme multilayer films based on the photoreaction of diazo-resins and glucose oxidase

    Energy Technology Data Exchange (ETDEWEB)

    Zhang Suxia [Key Lab of Supramolecular Structure and Materials, College of Chemistry, Jilin University, 119 Jie Fang Road, Changchun 130023 (China); Niu Yaming [Key Lab of Supramolecular Structure and Materials, College of Chemistry, Jilin University, 119 Jie Fang Road, Changchun 130023 (China); Sun Changqing [Key Lab of Supramolecular Structure and Materials, College of Chemistry, Jilin University, 119 Jie Fang Road, Changchun 130023 (China)]. E-mail: sunchq@mail.jlu.edu.cn

    2004-10-15

    A novel and facile approach to construct multilayered glucose oxidase (GOx) films on the surface of quartz or CaF{sub 2} slides as well as gold electrodes for use as biosensing interfaces is described. Diazo-resins (DAR) as polycation and glucose oxidase as polyanion were alternately deposited into a multilayer structure using layer-by-layer self-assembly technique based on electrostatic interaction as driving force. Upon near UV irradiation, the adjacent interfaces of the multilayer reacted to form a crosslinking structure which greatly improved the stability of the enzyme films. These changes was monitored and confirmed by UV-vis and IR spectroscopy. Ellipsometric measurements reveal that the enzymes formed sub-molecule layers, and the thickness of the film shows a linear relationship with the number of assembled layers, demonstrating a spatially well-ordered manner in multilayer structure. The covalently attached enzyme multilayer film has a highly permeable structure, and can be used as biosensing interface. Electrochemical and analytical behavior of the enzyme electrodes was studied by cyclic voltammetry (CV) in the presence or absence of glucose. The sensitivity of the enzyme-modified electrodes was estimated through the analysis of voltammetric signals, which can be fine turned to the desired level by adjusting the number of attached bilayers.

  1. New findings for the use of NMR- and computer tomography for gauging the potential of drilling fluids to cause damage to rocks; Neue Erkenntnisse bei der Anwendung von NMR- und Computertomografie-Methoden im Rahmen der Bewertung des Traegerschaedigungspotentiales von Bohrfluessigkeiten

    Energy Technology Data Exchange (ETDEWEB)

    Zwaag, C. van der [Reservoir Labs. AS, Trondheim (Norway); Stallmach, F. [Univ. Leipzig (Germany). Fakultaet fuer Physik und Geowissenschaften; Hanssen, J.E. [MI/Anchor Drilling Fluids AS, Stavanger (Norway); Soergaard, E. [Norsk Hydro AS, Bergen (Norway); Toennesen, R. [Saga Petroleum ASA, Stavanger (Norway)

    1998-12-31

    Polyanionic cellulose, xanthane and ppolyglycole are standard additives for water-based drilling fluids. These are added to drilling liquids to control water loss, provide viscosity and inhibit slating. Filtration losses, which are unavoidable when drilling, cause scavenging polymers to penetrate the area around the drilled hole. This causes a number of different reactions with the surrounding rocks and may ultimately have a permanent influence on the flow conditions of hydrocarbons. The study mentioned above aimed at determining the damage potential of these additives. [Deutsch] Polyanionische Cellulose, Xanthan und Polyglykol sind uebliche Zusatzstoffe von wasserbasischen Bohrspuelungen. Diese werden Bohrfluessigkeiten zur Wasserverlustkontrolle, zur Viskositaetsbildung und zur Schieferinhibierung zugesetzt. Die beim Bohrprozess unvermeidlichen Filtrationsverluste fuehren dazu, dass Spuelungspolymere beim Bohren in den Bohrlochnahbereich eindringen. Die Beschaffenheit dieser Stoffe fuehrt nach dem Eindringen zu unterschiedlichen Reaktionen mit dem Traegergestein. Diese koennen letzten Endes einen dauerhaften Einfluss auf die Zuflussbedingungen von Kohlenwasserstoffen haben. Das Ziel der vorliegenden Studie war es, das Traegerschaedigungspotential der obengenannten Spuelungszusaetze zu charakterisieren. (orig.)

  2. Interfacial characterization and supercapacitive properties of polyaniline-Gum arabic nanocomposite/graphene oxide LbL modified electrodes

    Science.gov (United States)

    Oliveira, Rafaela D.; Santos, Cleverson S.; Ferreira, Rodolfo T.; Marciniuk, Gustavo; Marchesi, Luís F.; Garcia, Jarem R.; Vidotti, Marcio; Pessoa, Christiana A.

    2017-12-01

    In this manuscript, we describe the synthesis and electrochemical characterization of polyaniline-gum arabic nanocomposites and graphene oxide (PANI-GA/GO) modified electrodes with a detailed study concerning their supercapacitive properties. The electrode modification was carried out by using the Layer-by-Layer technique (LbL), where the PANI-GA nanocomposite dispersion was used as polycation and the GO colloidal dispersion as polyanion. The bilayer growth was followed by both UV-vis spectroscopy and cyclic voltammetry, and an increase in the characteristic PANI absorption and in the electrochemical signal was verified, confirming the electrode build up. Galvanostatic charge-discharge curves (GCDC) were performed to evaluate the supercapacitive properties of the modified electrodes, these results showed the dependence of the specific capacitance with the number of bilayers, where values of CS around 15 mF cm-2 (i = 0.1 mA cm-2) were found. Electrochemical impedance spectroscopy confirmed the pseudocapacitive properties of the modified electrodes, showing an increase in the low-frequency capacitance with the number of bilayers. Hereby the (PANI-GA/GO)-LbL electrodes were shown to be good candidates for active materials in supercapacitors.

  3. Cationic liposome/DNA complexes: from structure to interactions with cellular membranes.

    Science.gov (United States)

    Caracciolo, Giulio; Amenitsch, Heinz

    2012-10-01

    Gene-based therapeutic approaches are based upon the concept that, if a disease is caused by a mutation in a gene, then adding back the wild-type gene should restore regular function and attenuate the disease phenotype. To deliver the gene of interest, both viral and nonviral vectors are used. Viruses are efficient, but their application is impeded by detrimental side-effects. Among nonviral vectors, cationic liposomes are the most promising candidates for gene delivery. They form stable complexes with polyanionic DNA (lipoplexes). Despite several advantages over viral vectors, the transfection efficiency (TE) of lipoplexes is too low compared with those of engineered viral vectors. This is due to lack of knowledge about the interactions between complexes and cellular components. Rational design of efficient lipoplexes therefore requires deeper comprehension of the interactions between the vector and the DNA as well as the cellular pathways and mechanisms involved. The importance of the lipoplex structure in biological function is revealed in the application of synchrotron small-angle X-ray scattering in combination with functional TE measurements. According to current understanding, the structure of lipoplexes can change upon interaction with cellular membranes and such changes affect the delivery efficiency. Recently, a correlation between the mechanism of gene release from complexes, the structure, and the physical and chemical parameters of the complexes has been established. Studies aimed at correlating structure and activity of lipoplexes are reviewed herein. This is a fundamental step towards rational design of highly efficient lipid gene vectors.

  4. Microbial exopolysaccharide-mediated synthesis and stabilization of metal nanoparticles.

    Science.gov (United States)

    Sathiyanarayanan, Ganesan; Dineshkumar, Krishnamoorthy; Yang, Yung-Hun

    2017-11-01

    Exopolysaccharides (EPSs) are structurally and functionally valuable biopolymer secreted by different prokaryotic and eukaryotic microorganisms in response to biotic/abiotic stresses and to survive in extreme environments. Microbial EPSs are fascinating in various industrial sectors due to their excellent material properties and less toxic, highly biodegradable, and biocompatible nature. Recently, microbial EPSs have been used as a potential template for the rapid synthesis of metallic nanoparticles and EPS-mediated metal reduction processes are emerging as simple, harmless, and environmentally benign green chemistry approaches. EPS-mediated synthesis of metal nanoparticles is a distinctive metabolism-independent bio-reduction process due to the formation of interfaces between metal cations and the polyanionic functional groups (i.e. hydroxyl, carboxyl and amino groups) of the EPS. In addition, the range of physicochemical features which facilitates the EPS as an efficient stabilizing or capping agents to protect the primary structure of the metal nanoparticles with an encapsulation film in order to separate the nanoparticle core from the mixture of composites. The EPS-capping also enables the further modification of metal nanoparticles with expected material properties for multifarious applications. The present review discusses the microbial EPS-mediated green synthesis/stabilization of metal nanoparticles, possible mechanisms involved in EPS-mediated metal reduction, and application prospects of EPS-based metal nanoparticles.

  5. Construction of covalently attached enzyme multilayer films based on the photoreaction of diazo-resins and glucose oxidase

    International Nuclear Information System (INIS)

    Zhang Suxia; Niu Yaming; Sun Changqing

    2004-01-01

    A novel and facile approach to construct multilayered glucose oxidase (GOx) films on the surface of quartz or CaF 2 slides as well as gold electrodes for use as biosensing interfaces is described. Diazo-resins (DAR) as polycation and glucose oxidase as polyanion were alternately deposited into a multilayer structure using layer-by-layer self-assembly technique based on electrostatic interaction as driving force. Upon near UV irradiation, the adjacent interfaces of the multilayer reacted to form a crosslinking structure which greatly improved the stability of the enzyme films. These changes was monitored and confirmed by UV-vis and IR spectroscopy. Ellipsometric measurements reveal that the enzymes formed sub-molecule layers, and the thickness of the film shows a linear relationship with the number of assembled layers, demonstrating a spatially well-ordered manner in multilayer structure. The covalently attached enzyme multilayer film has a highly permeable structure, and can be used as biosensing interface. Electrochemical and analytical behavior of the enzyme electrodes was studied by cyclic voltammetry (CV) in the presence or absence of glucose. The sensitivity of the enzyme-modified electrodes was estimated through the analysis of voltammetric signals, which can be fine turned to the desired level by adjusting the number of attached bilayers

  6. Ion distribution in dry polyelectrolyte multilayers: a neutron reflectometry study.

    Science.gov (United States)

    Ghoussoub, Yara E; Zerball, Maximilian; Fares, Hadi M; Ankner, John F; von Klitzing, Regine; Schlenoff, Joseph B

    2018-02-28

    Ultrathin films of complexed polycation poly(diallyldimethylammonium), PDADMA, and polyanion poly(styrenesulfonate), PSS, were prepared on silicon wafers using the layer-by-layer adsorption technique. When terminated with PDADMA, all films had excess PDADMA, which was balanced by counterions. Neutron reflectivity of these as-made multilayers was compared with measurements on multilayers which had been further processed to ensure 1 : 1 stoichiometry of PDADMA and PSS. The compositions of all films, including polymers and counterions, were determined experimentally rather than by fitting, reducing the number of fit parameters required to model the reflectivity. For each sample, acetate, either protiated, CH 3 COO - , or deuterated, CD 3 COO - , served as the counterion. All films were maintained dry under vacuum. Scattering length density profiles were constrained to fit reflectivity data from samples having either counterion. The best fits were obtained with uniform counterion concentrations, even for stoichiometric samples that had been exposed to PDADMA for ca. 5 minutes, showing that surprisingly fast and complete transport of excess cationic charge occurs throughout the multilayer during its construction.

  7. The Non-Hemostatic Aspects of Transfused Platelets

    Directory of Open Access Journals (Sweden)

    Caroline Sut

    2018-02-01

    Full Text Available Platelets transfusion is a safe process, but during or after the process, the recipient may experience an adverse reaction and occasionally a serious adverse reaction (SAR. In this review, we focus on the inflammatory potential of platelet components (PCs and their involvement in SARs. Recent evidence has highlighted a central role for platelets in the host inflammatory and immune responses. Blood platelets are involved in inflammation and various other aspects of innate immunity through the release of a plethora of immunomodulatory cytokines, chemokines, and associated molecules, collectively termed biological response modifiers that behave like ligands for endothelial and leukocyte receptors and for platelets themselves. The involvement of PCs in SARs—particularly on a critically ill patient’s context—could be related, at least in part, to the inflammatory functions of platelets, acquired during storage lesions. Moreover, we focus on causal link between platelet activation and immune-mediated disorders (transfusion-associated immunomodulation, platelets, polyanions, and bacterial defense and alloimmunization. This is linked to the platelets’ propensity to be activated even in the absence of deliberate stimuli and to the occurrence of time-dependent storage lesions.

  8. Photoresponsive layer-by-layer ultrathin films prepared from a hyperbranched azobenzene-containing polymeric diazonium salt

    International Nuclear Information System (INIS)

    Li Xinyang; Fan Pengwei; Tuo Xinlin; He Yaning; Wang Xiaogong

    2009-01-01

    In this work, a hyperbranched diazonium salt (HB-DAS), prepared through azo-coupling reaction of an AB 2 monomer (N, N-bis[2-(4-aminobenzoyloxy)ethyl]aniline), was used to prepare self-assembled multilayers and ultrathin films. Multilayer films were fabricated by dipping substrates in HB-DAS and other polyelectrolyte solutions alternately in a layer-by-layer (LBL) manner. It was somewhat surprising to observe that HB-DAS forms multilayer films with either a polyanion (poly(styrenesulfonate sodium salt), PSS) or a polycation (poly(diallyldimethylammonium chloride), PDAC) through alternate deposition in the solutions. Ultrathin films were formed in a sequential growth manner by dipping the substrates in the HB-DAS solution, washing with deionized water and drying repeatedly. In all the processes, the absorbance and thickness of the thin films linearly increase as the number of the dipping cycle increases. HB-DAS/PSS multilayer possesses an obviously larger bilayer thickness and lower density compared with the other two counterparts. The drying step after each deposition is necessary for the HB-DAS ultrathin film growth through the repeated dip-coating of HB-DAS. The multilayer and ultrathin films prepared by the above methods all show high resistance to erosion by organic solvents. The multilayers and ultrathin films exhibit photoinduced dichroism upon the irradiation of a polarized Ar + laser beam

  9. Photoresponsive layer-by-layer ultrathin films prepared from a hyperbranched azobenzene-containing polymeric diazonium salt

    Energy Technology Data Exchange (ETDEWEB)

    Li Xinyang; Fan Pengwei; Tuo Xinlin; He Yaning [Department of Chemical Engineering, Laboratory for Advanced Materials, Tsinghua University, Beijing, 100084 (China); Wang Xiaogong [Department of Chemical Engineering, Laboratory for Advanced Materials, Tsinghua University, Beijing, 100084 (China)], E-mail: wxg-dce@mail.tsinghua.edu.cn

    2009-01-30

    In this work, a hyperbranched diazonium salt (HB-DAS), prepared through azo-coupling reaction of an AB{sub 2} monomer (N, N-bis[2-(4-aminobenzoyloxy)ethyl]aniline), was used to prepare self-assembled multilayers and ultrathin films. Multilayer films were fabricated by dipping substrates in HB-DAS and other polyelectrolyte solutions alternately in a layer-by-layer (LBL) manner. It was somewhat surprising to observe that HB-DAS forms multilayer films with either a polyanion (poly(styrenesulfonate sodium salt), PSS) or a polycation (poly(diallyldimethylammonium chloride), PDAC) through alternate deposition in the solutions. Ultrathin films were formed in a sequential growth manner by dipping the substrates in the HB-DAS solution, washing with deionized water and drying repeatedly. In all the processes, the absorbance and thickness of the thin films linearly increase as the number of the dipping cycle increases. HB-DAS/PSS multilayer possesses an obviously larger bilayer thickness and lower density compared with the other two counterparts. The drying step after each deposition is necessary for the HB-DAS ultrathin film growth through the repeated dip-coating of HB-DAS. The multilayer and ultrathin films prepared by the above methods all show high resistance to erosion by organic solvents. The multilayers and ultrathin films exhibit photoinduced dichroism upon the irradiation of a polarized Ar{sup +} laser beam.

  10. Micellar effect on the sensitivity of spectrophotometric Mo(VI) determination based on the formation of gallic acid complex providing evidence for the polyoxoanion structure of molybdate ions

    International Nuclear Information System (INIS)

    Tascioglu, Senay; Sendil, Olcay; Beyreli, Sivekar

    2007-01-01

    In this study effects of anionic (sodium dodecyl sulfate, SDS), cationic (cetyltrimethylammonium bromide, CTAB) and nonionic (Triton X-100, TX100) micelles on the sensitivity of spectrophotometric molybdenum(VI) (Mo) determination based on the formation of a binary complex with gallic acid (GA) were investigated. Micellar CTAB was found to enhance the formation of Mo-GA complex. SDS micelles exerted an inhibitory effect while TX100 micelles had no effect on the complex formation. By the optimization of experimental conditions, the determination limit of the method suggested in the literature was lowered from 5.2 x 10 -5 to 4.6 x 10 -6 and to 5.7 x 10 -7 M, in the absence and presence of CTAB, respectively. The mechanism of the effect of CTAB was investigated by spectrophotometric titrations and it was concluded that CTAB did not form a ternary complex with Mo and GA. The stoichiometry of the complex, deduced from the results of spectrophotometric titrations, provided evidence for the formation of para-Mo 7 O 4 6- polyanions at pH 4.5, indicating to the formation of a charge transfer complex between these ions and GA in micellar medium

  11. Cigarette smoke decreases mitochondrial porin expression and steroidogenesis

    International Nuclear Information System (INIS)

    Bose, Mahuya; Whittal, Randy M.; Gairola, C. Gary; Bose, Himangshu S.

    2008-01-01

    Steroidogenic acute regulatory protein (StAR) facilitates the movement of cholesterol from the outer to inner mitochondrial membrane for steroidogenesis. Here, we investigated the effect of cigarette smoke (CS) on steroidogenesis using adrenal mitochondria isolated from mice chronically exposed to CS. Steroidogenesis was decreased approximately 78% in CS-exposed mitochondria, as measured by synthesis of the steroid hormone precursor pregnenolone. This effect was accompanied by decreased mitochondrial import of 35 S-StAR. Further characterization of the imported 35 S-StAR by native gradient PAGE revealed the presence of a high molecular weight complex in both control and CS-exposed groups. Following density gradient fractionation of 35 S-StAR that had been extracted from control mitochondria, precursor StAR could be found in fractions 2-6 and smaller-sized StAR complexes in fractions 6-13. In the CS-exposed group, the appearance of precursor shifted from fraction 1-6 and the smaller complexes in fractions 6-9 disappeared. Mass spectrometric analysis revealed that the 35 S-StAR-associated protein complex was composed of several resident matrix proteins as well as the OMM resident, VDAC. VDAC expression was greatly reduced by CS, and blockage of VDAC with Koenig's polyanion decreased pregnenolone synthesis in isolated mitochondria. Taken together, these results suggest that VDAC may participate in steroidogenesis by promoting StAR interaction with the OMM and that CS may inhibit steroidogenesis by reducing VDAC-StAR interactions

  12. pH-sensitive polymeric nanoparticles to improve oral bioavailability of peptide/protein drugs and poorly water-soluble drugs.

    Science.gov (United States)

    Wang, Xue-Qing; Zhang, Qiang

    2012-10-01

    pH-sensitive polymeric nanoparticles are promising for oral drug delivery, especially for peptide/protein drugs and poorly water-soluble medicines. This review describes current status of pH-sensitive polymeric nanoparticles for oral drug delivery and introduces the mechanisms of drug release from them as well as possible reasons for absorption improvement, with emphasis on our contribution to this field. pH-sensitive polymeric nanoparticles are prepared mainly with polyanions, polycations, their mixtures or cross-linked polymers. The mechanisms of drug release are the result of carriers' dissolution, swelling or both of them at specific pH. The possible reasons for improvement of oral bioavailability include the following: improve drug stability, enhance mucoadhesion, prolong resident time in GI tract, ameliorate intestinal permeability and increase saturation solubility and dissolution rate for poorly water-soluble drugs. As for the advantages of pH-sensitive nanoparticles over conventional nanoparticles, we conclude that (1) most carriers used are enteric-coating materials and their safety has been approved. (2) The rapid dissolution or swelling of carriers at specific pH results in quick drug release and high drug concentration gradient, which is helpful for absorption. (3) At the specific pH carriers dissolve or swell, and the bioadhesion of carriers to mucosa becomes high because nanoparticles turn from solid to gel, which can facilitate drug absorption. Copyright © 2012 Elsevier B.V. All rights reserved.

  13. Magnetic resonance as a structural probe of a uranium (VI) sol-gel process

    International Nuclear Information System (INIS)

    King, C.M.; Thompson, M.C.; Buchanan, B.R.; King, R.B.; Garber, A.R.

    1989-01-01

    NMR investigations on the ORNL process for sol-gel synthesis of microspherical nuclear fuel (UO 2 ), has been useful in sorting out the chemical mechanism in the sol-gel steps. 13 C, 15 N, and 1 H NMR studies on the HMTA gelation agent (Hexamethylene tetramine, C 6 H l2 N 4 ) has revealed near quantitative stability of this adamantane-like compound in the sol-Gel process, contrary to its historical role as an ammonia source for gelation from the worldwide technical literature. 17 0 NMR of uranyl (UO 2 ++ ) hydrolysis fragments produced in colloidal sols has revealed the selective formation of a uranyl trimer, [(UO 2 ) 3 (μ 3 -O)(μ 2 -OH) 3 ] + , induced by basic hydrolysis with the HMTA gelation agent. Spectroscopic results show that trimer condensation occurs during sol-gel processing leading to layered polyanionic hydrous uranium oxides in which HMTAH + is occluded as an ''intercalation'' cation. Subsequent sol-gel processing of microspheres by ammonia washing results in in-situ ion exchange and formation of a layered hydrous ammonium uranate with a proposed structural formula of (NH 4 ) 2 [(UO 2 ) 8 O 4 (OH) 10 ] · 8H 2 0. This compound is the precursor to sintered U0 2 ceramic fuel

  14. New insights into uranium (VI) sol-gel processing

    International Nuclear Information System (INIS)

    King, C.M.; Thompson, M.C.; Buchanan, B.R.; King, R.B.; Garber, A.R.

    1990-01-01

    Nuclear Magnetic Resonance (NMR) investigations on the Oak Ridge National Laboratory process for sol-gel synthesis of microspherical nuclear fuel (UO 2 ), has been extremely useful in sorting out the chemical mechanism in the sol-gel steps. 13 C, 15 N, and 1 H NMR studies on the HMTA gelation agent (Hexamethylene tetramine, C 6 H 12 N 4 ) has revealed near quantitative stability of this adamantane-like compound in the sol-gel process, contrary to its historical role as an ammonia source for gelation from the worldwide technical literature. 17 O NMR of uranyl (UO 2 ++ ) hydrolysis fragments produced in colloidal sols has revealed the selective formation of a uranyl trimer, [(UO 2 ) 3 (μ 3 -O)(μ 2 -OH) 3 ] + , induced by basic hydrolysis with the HMTA gelation agent. Spectroscopic results will be presented to illustrate that trimer condensation occurs during sol-gel processing leading to layered polyanionic hydrous uranium oxides in which HMTAH + is occluded as an ''intercalation'' cation. Subsequent sol-gel processing of microspheres by ammonia washing results in in-situ exchange and formation of a layered hydrous ammonium uranate with a proposed structural formula of (NH 4 ) 2 [(UO 2 ) 8 O 4 (OH) 10 ] · 8H 2 O. This compound is the precursor to sintered UO 2 ceramic fuel. 23 refs., 10 figs

  15. Study and Optimization of Self-Assembled Polymeric Multilayer Structures with Neutral Red for pH Sensing Applications

    Directory of Open Access Journals (Sweden)

    Javier Goicoechea

    2008-01-01

    Full Text Available The characterization of nanostructured thin films is critical in the design and fabrication of optical sensors. Particularly, this work is a detailed study of the properties of layer-by-layer electrostatic self-assembled multilayer (LbL structures fabricated using poly(allylamine hydrochloride (PAH and Neutral Red (NR as cations, and poly(acrylic acid (PAA as polyanion. These LbL films, due to the colorimetric properties of the NR, are suitable for sensor applications such as pH sensing in the physiological range. In the (PAH+NR/PAA LbL structure, it has been observed a very important influence of the pH of the solutions in the properties of the resultant films. Different techniques such as spectroscopy and atomic force microscopy (AFM are combined to characterize the films, and the results are analyzed showing coherence with previous works. The LbL structure is finally optimized and dramatically improved nanostructured films were fabricated, showing good sensing properties, short response times, and good stability.

  16. Electrochemical supercapacitors based on novel hybrid materials made of carbon nanotubes and polyoxometalates

    Energy Technology Data Exchange (ETDEWEB)

    Cuentas-Gallegos, Ana Karina; Martinez-Rosales, Rosa; Rincon, Marina E. [Centro de Investigacion en Energia, Universidad Nacional Autonoma de Mexico, Priv. Xochicalco s/n, Col. Centro, C.P. 62580 Temixco, Mor (Mexico); Baibarac, Mihaela; Gomez-Romero, Pedro [Instituto de Ciencia de Materiales de Barcelona, CSIC, Campus de la UAB, 08193 Bellaterra (Spain)

    2007-08-15

    We have characterized symmetric solid-state supercapacitors in swagelok cells using film electrodes made of novel hybrid materials based on multiwalled carbon nanotubes (CNT) and phosphomolybdate polyanion (Cs-PMo12) with PVA as binder. These hybrid materials were carried out by Cs-PMo12 adhesion onto previously functionalized CNT, in order to disperse both components at a molecular level and use Cs-PMo12 as energy density enhancer in supercapacitor cells. Our results show high capacitance values (up to 285 F/g at I = 200 mA/g) due to the contribution of Cs-PMo12, which was revealed on the higher energy density values compared to pure CNT electrodes. Additionally, good stability was observed during 500 charge-discharge cycles for most hybrid electrodes. These preliminary results show a new approach to enhance energy density of double layer supercapacitor cells through the introduction of Cs-PMo12, whereas from a material science point of view these materials are innovative, and open the way to search for diverse applications aside from supercapacitors (sensors, catalysts, photovoltaic cells, etc.). (author)

  17. Reorganization of the 3D matrix of polyelectrolytes complexes of chitosan/chondroitin sulfate swollen in different conditions of pH and immersion time

    International Nuclear Information System (INIS)

    Fajardo, Andre R.; Piai, Juliana F.; Rubira, Adley F.; Muniz, Edvani C.

    2009-01-01

    The chitosan (CT), a polysaccharide that has excellent properties for use as biomaterials, shows cationic nature and properties of high charge density in acidic solutions, thus CT can form complex polyelectrolyte (PEC) with polyanionic moieties such as the chondroitin sulfate (CS), a key component of cartilage matrix. We studied the reorganization of chains on 3D matrix of CT/CS PEC at swollen state in different conditions of pH and immersion time. It was verified that this PEC (QT/CS) has the capacity to reorganize its 3D matrix but it depends of the pH of the medium in which it is swelled and the time that remains immersed. The reorganization of the 3D matrix is caused by the reordering of the chains forming the PEC after the release of the CS, that occurs mainly at pH values higher than or close to the pKa of CT (pKa CT) . Such reorganization was detected by X-ray diffraction profiles and allows an increase in crystallinity, thermal stability and pore size of the PEC. This shows that the PEC produced can be processed to suit its use as bio material, applied i.e. as drugs release devices. (author)

  18. Manual and Flow-Injection Detection/Quantification of Polyquaterniums via Fully Reversible Polyion-Sensitive Polymeric Membrane-Based Ion-Selective Electrodes.

    Science.gov (United States)

    Ferguson, Stephen A; Meyerhoff, Mark E

    2017-10-27

    The detection of four different polyquaterniums (PQs) using a fully reversible potentiometric polyion sensor in three different detection modes is described. The polyion sensing "pulstrodes" serve as the detector for direct dose-response experiments, beaker titrations, and in a flow-injection analysis (FIA) system. Direct polycation response toward PQ-2, PQ-6, PQ-10, and poly(2-methacryloxyethyltrimethylammonium) chloride (PMETAC) yields characteristic information about each PQ species (e.g., relative charge densities, etc.) via syringe pump addition of each PQ species to a background electrolyte solution. Quantitative titrations are performed using a syringe pump to deliver heparin as the polyanion titrant to quantify all four PQs at μg/mL levels. Both the direct and indirect methods incorporate the use of a three-electrode system including counter, double junction reference, and working electrodes. The working electrode possesses a plasticized poly(vinyl chloride) (PVC) membrane containing the neutral lipophilic salt of dinonylnaphthalenesulfonate (DNNS - ) tridodecylmethylammonium (TDMA + ). Further, the titration method is shown to be useful to quantify PQ-6 levels in recreational swimming pool water collected in Ann Arbor, MI. Finally, a FIA system equipped with a pulstrode detector is used to demonstrate the ability to potentially quantify PQ levels via a more streamlined and semiautomated testing platform.

  19. Virus-mimetic polyplex particles for systemic and inflammation-specific targeted delivery of large genetic contents.

    Science.gov (United States)

    Kang, S; Lu, K; Leelawattanachai, J; Hu, X; Park, S; Park, T; Min, I M; Jin, M M

    2013-11-01

    Systemic and target-specific delivery of large genetic contents has been difficult to achieve. Although viruses effortlessly deliver kilobase-long genome into cells, its clinical use has been hindered by serious safety concerns and the mismatch between native tropisms and desired targets. Nonviral vectors, in contrast, are limited by low gene transfer efficiency and inherent cytotoxicity. Here we devised virus-mimetic polyplex particles (VMPs) based on electrostatic self-assembly among polyanionic peptide (PAP), cationic polymer polyethyleneimine (PEI) and nucleic acids. We fused PAP to the engineered ligand-binding domain of integrin αLβ2 to target intercellular adhesion molecule-1 (ICAM-1), an inducible marker of inflammation. Fully assembled VMPs packaged large genetic contents, bound specifically to target molecules, elicited receptor-mediated endocytosis and escaped endosomal pathway, resembling intracellular delivery processes of viruses. Unlike conventional PEI-mediated transfection, molecular interaction-dependent gene delivery of VMPs was unaffected by the presence of serum and achieved higher efficiency without toxicity. By targeting overexpressed ICAM-1, VMPs delivered genes specifically to inflamed endothelial cells and macrophages both in vitro and in vivo. Simplicity and versatility of the platform and inflammation-specific delivery may open up opportunities for multifaceted gene therapy that can be translated into the clinic and treat a broad range of debilitating immune and inflammatory diseases.

  20. Polyion selective polymeric membrane-based pulstrode as a detector in flow-injection analysis.

    Science.gov (United States)

    Bell-Vlasov, Andrea K; Zajda, Joanna; Eldourghamy, Ayman; Malinowska, Elzbieta; Meyerhoff, Mark E

    2014-04-15

    A method for the detection of polyions using fully reversible polyion selective polymeric membrane type pulstrodes as detectors in a flow-injection analysis (FIA) system is examined. The detection electrode consists of a plasticized polymeric membrane doped with 10 wt % of tridodecylmethylammonium-dinonylnaphthalene sulfonate (TDMA/DNNS) ion-exchanger salt. The pulse sequence used involves a short (1 s) galvanostatic pulse, an open-circuit pulse (0.5 s) during which the EMF of the cell is measured, and a longer (15 s) potentiostatic pulse to return the membrane to its original chemical composition. It is shown that total pulse sequence times can be optimized to yield reproducible real-time detection of injected samples of protamine and heparin at up to 20 samples/h. Further, it is shown that the same membrane detector can be employed for FIA detection of both polycations at levels ≥10 μg/mL and polyanions at levels of ≥40 μg/mL by changing the direction of the galvanostatic pulse. The methodology described may also be applicable in the detection of polyionic species at low levels in other flowing configurations, such as in liquid chromatography and capillary electrophoresis.

  1. Copper sulfates as cathode materials for Li batteries

    Energy Technology Data Exchange (ETDEWEB)

    Schwieger, Jonathan N.; Kraytsberg, Alexander; Ein-Eli, Yair [Technion Israel Institute of Technology, Department of Materials Engineering, Technion City, Haifa 32000 (Israel)

    2011-02-01

    As lithium battery technology sets out to bridge the gap between portable electronics and the electrical automotive industry, cathode materials still stand as the bottleneck regarding performances. In the realm of highly attractive polyanion-type structures as high-voltage cathode materials, the sulfate group (SO{sub 4}){sup 2-} possesses an acknowledged superiority over other contenders in terms of open circuit voltage arising from the inductive effect of strong covalent S-O bonds. In parallel, novel lithium insertion mechanisms are providing alternatives to traditional intercalation, enabling reversible multi-electron processes securing high capacities. Combining both of these advantageous features, we report here the successful electrochemical reactivity of copper sulfate pentahydrate (CuSO{sub 4}.5H{sub 2}O) with respect to lithium insertion via a two-electron displacement reaction entailing the extrusion of metallic copper at a dual voltage of 3.2 V and 2.7 V followed by its reversible insertion at 3.5 V and 3.8 V. At this stage, cyclability was still shown to be limited due to the irreversible degradation to a monohydrate structure owing to constitutional water loss. (author)

  2. Bioemulsan Production by Iranian Oil Reservoirs Microorganisms

    Directory of Open Access Journals (Sweden)

    A Amiriyan, M Mazaheri Assadi, VA Saggadian, A Noohi

    2004-10-01

    Full Text Available The biosurfactants are believed to be surface active components that are shed into the surrounding medium during the growth of the microorganisms. The oil degrading microorganism Acinetobacter calcoaceticus RAG-1 produces a poly-anionic biosurfactant, hetero-polysaccharide bioemulsifier termed as emulsan which forms and stabilizes oil-water emulsions with a variety of hydrophobic substrates. In the present paper results of the possibility of biosurfactant (Emulsan production by microorganisms isolated from Iranian oil reservoirs is presented. Fourthy three gram negative and gram positive, non fermentative, rod bacilli and coccobacilli shaped baceria were isolated from the oil wells of Bibi Hakimeh, Siri, Maroon, Ilam , East Paydar and West Paydar. Out of the isolated strains, 39 bacterial strains showed beta haemolytic activity, further screening revealed the emulsifying activity and surface tension. 11 out of 43 tested emulsifiers were identified as possible biosurfactant producers and two isolates produced large surface tension reduction, indicating the high probability of biosurfactant production. Further investigation revealed that, two gram negative, oxidase negative, aerobic and coccoid rods isolates were the best producers and hence designated as IL-1, PAY-4. Whole culture broth of isolates reduced surface tension from 68 mN /m to 30 and 29.1mN/m, respectively, and were stable during exposure to high salinity (10%NaCl and elevated temperatures(120C for 15 min .

  3. Prevention of H-Aggregates Formation in Cy5 Labeled Macromolecules

    Directory of Open Access Journals (Sweden)

    Jing Kang

    2010-01-01

    Full Text Available H-aggregates of the cyanine dye Cy5 are formed during covalent linkage to the cationic macromolecule Poly(allylamine (PAH. The nonfluorescent H-aggregates strongly restrict the usage of the dye for analytical purposes and prevent a quantitative determination of the labeled macromolecules. The behavior of the H-aggregates has been studied by investigation of the absorption and fluorescence spectra of the dye polymer in dependence on solvent, label degree and additional sulfonate groups. H-aggregate formation is caused by an inhomogeneous distribution of the Cy5 molecules on the polymer chain. The H-aggregates can be destroyed by conformational changes of the PAH induced by interactions with polyanions or in organic solvents. It has been found that the polymer labeling process in high content of organic solvents can prevent the formation of H-aggregates. The results offer a better understanding and improvement of the use of the Cy5 dye for labeling purposes in fluorescence detection of macromolecules.

  4. Effect of heat shock on poly(ADP-ribose) synthetase and DNA repair in Drosophila cells

    Energy Technology Data Exchange (ETDEWEB)

    Nolan, N.L.; Kidwell, W.R.

    1982-04-01

    Poly(ADP-ribose) synthetase, a chromatin-bound enzyme which attaches polyanionic chains of ADP-ribose to nuclear proteins, was found to be temperature sensitive in intact Drosophila melanogaster cells. The synthetase was completely inactivated by heat-shocking the cells at 37/sup 0/C for 5 min, a condition which had no appreciable effect on the subsequent growth of Drosophila cells at their physiological temperature. The heat-shock effect on synthetase was reversible; enzyme activity began to reappear about 2 hr post heat shock. During the 2-hr interval when poly(ADP-ribose) synthetase was absent, the cells were competent in repair of ..gamma..-ray-induced DNA strand breaks as shown by DNA sedimentation studies on alkaline sucrose gradients. It is thus concluded that poly(ADP-ribose) synthesis is unnecessary for repair of DNA strand breaks introduced by irradiation. The same conclusion was reached from the fact that two inhibitors of poly(ADP-ribose) synthetase 3-aminobenzamide and 5-methylnicotinamide, failed to block repair of ..gamma..-ray-induced DNA chain breaks even though both inhibitors reduced the amount of poly(ADP-ribose) synthesized in cells by 50-75%. Although it was found that the repair of DNA strand breaks is independent of poly(ADP-ribose) synthesis, irradiation does activate the synthetase in control cells, as shown by radioimmunoassay of poly(ADP-ribose) levels.

  5. Effect of heat shock on poly(ADP-ribose) synthetase and DNA repair in Drosophila cells

    International Nuclear Information System (INIS)

    Nolan, N.L.; Kidwell, W.R.

    1982-01-01

    Poly(ADP-ribose) synthetase, a chromatin-bound enzyme which attaches polyanionic chains of ADP-ribose to nuclear proteins, was found to be temperature sensitive in intact Drosophila melanogaster cells. The synthetase was completely inactivated by heat-shocking the cells at 37 0 C for 5 min, a condition which had no appreciable effect on the subsequent growth of Drosophila cells at their physiological temperature. The heat-shock effect on synthetase was reversible; enzyme activity began to reappear about 2 hr post heat shock. During the 2-hr interval when poly(ADP-ribose) synthetase was absent, the cells were competent in repair of γ-ray-induced DNA strand breaks as shown by DNA sedimentation studies on alkaline sucrose gradients. It is thus concluded that poly(ADP-ribose) synthesis is unnecessary for repair of DNA strand breaks introduced by irradiation. The same conclusion was reached from the fact that two inhibitors of poly(ADP-ribose) synthetase 3-aminobenzamide and 5-methylnicotinamide, failed to block repair of γ-ray-induced DNA chain breaks even though both inhibitors reduced the amount of poly(ADP-ribose) synthesized in cells by 50-75%. Although it was found that the repair of DNA strand breaks is independent of poly(ADP-ribose) synthesis, irradiation does activate the synthetase in control cells, as shown by radioimmunoassay of poly(ADP-ribose) levels

  6. Using Biomimetic Polymers in Place of Noncollagenous Proteins to Achieve Functional Remineralization of Dentin Tissues

    Energy Technology Data Exchange (ETDEWEB)

    Chien, Yung-Ching [Molecular; Department; Tao, Jinhui [Molecular; Physical; Saeki, Kuniko [Department; Chin, Alexander F. [Department; Lau, Jolene L. [Molecular; Chen, Chun-Long [Molecular; Physical; Zuckermann, Ronald N. [Molecular; Marshall, Sally J. [Department; Marshall, Grayson W. [Department; De Yoreo, James J. [Molecular; Physical; Department

    2017-11-16

    In calcified tissues such as bones and teeth, mineralization is regulated by an extracellular matrix, which includes non-collagenous proteins (NCP). This natural process has been adapted or mimicked to restore tissues following physical damage or demineralization by using polyanionic acids in place of NCPs, but the remineralized tissues fail to fully recover their mechanical properties. Here we show that pre-treatment with certain amphiphilic peptoids, a class of peptide-like polymers consisting of N-substituted glycines that have defined monomer sequences, enhances ordering and mineralization of collagen and induces functional remineralization of dentin lesions in vitro. In the vicinity of dentin tubules, the newly formed apatite nano-crystals are co-aligned with the c-axis parallel to the tubular periphery and recovery of tissue ultrastructure is accompanied by development of high mechanical strength. The observed effects are highly sequence-dependent with alternating polar and non-polar groups leading to positive outcomes while diblock sequences have no effect. The observations suggest aromatic groups interact with the collagen while the hydrophilic side chains bind the mineralizing constituents and highlight the potential of synthetic sequence-defined biomimetic polymers to serve as NCP mimics in tissue remineralization.

  7. Several new phases in RE-Mg-Ge systems (RE = rare earth metal) - syntheses, structures, and chemical bonding

    International Nuclear Information System (INIS)

    Suen, Nian-Tzu; Bobev, Svilen

    2012-01-01

    Reported are the synthesis and structural characterization of Ce_5Mg_8Ge_8 (its own structure type), CeMg_2_-_xGe_2_+_x (BaAl_4-type structure), RE_4Mg_7Ge_6 (RE = Ce-Nd, Sm; La_4Mg_7Ge_6-type structure), and RE_4Mg_5Ge_6 (RE = Ce, Pr; Tm_4Zn_5Ge_6-type structure). The structures of these compounds have been established by single-crystal and powder X-ray diffraction. These compounds are closely related to each other not only in their chemical compositions but also in their structures. A common structural feature of all are MgGe_4 tetrahedra, which are connected by corner- and/or edge-sharing into complex polyanionic frameworks with the rare-earth metal atoms filling the ''empty'' space. The structures are compared to known types of structures, and we have investigated the chemical bonding in Ce_5Mg_8Ge_8 with electronic structure calculations, which were carried out by the tight-bonding linear muffin-tin orbital (TB-LMTO) method. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  8. Optimization of the Use of His₆-OPH-Based Enzymatic Biocatalysts for the Destruction of Chlorpyrifos in Soil.

    Science.gov (United States)

    Senko, Olga; Maslova, Olga; Efremenko, Elena

    2017-11-23

    Applying enzymatic biocatalysts based on hexahistidine-containing organophosphorus hydrolase (His₆-OPH) is suggested for the decomposition of chlorpyrifos, which is actively used in agriculture in many countries. The application conditions were optimized and the following techniques was suggested to ensure the highest efficiency of the enzyme: first, the soil is alkalinized with hydrated calcitic lime Ca(OH)₂, then the enzyme is introduced into the soil at a concentration of 1000 U/kg soil. Non-equilibrium low temperature plasma (NELTP)-modified zeolite is used for immobilization of the relatively inexpensive polyelectrolyte complexes containing the enzyme His₆-OPH and a polyanionic polymer: poly-l-glutamic acid (PLE 50 ) or poly-l-aspartic acid (PLD 50 ). The soil's humidity is then increased up to 60-80%, the top layer (10-30 cm) of soil is thoroughly stirred, and then exposed for 48-72 h. The suggested approach ensures 100% destruction of the pesticide within 72 h in soils containing as much as 100 mg/kg of chlorpyrifos. It was concluded that using this type of His₆-OPH-based enzyme chemical can be the best approach for soils with relatively low humus concentrations, such as sandy and loam-sandy chestnut soils, as well as types of soil with increased alkalinity (pH 8.0-8.4). Such soils are often encountered in desert, desert-steppe, foothills, and subtropical regions where chlorpyrifos is actively used.

  9. Current insights into the laboratory diagnosis of HIT.

    Science.gov (United States)

    Bakchoul, T; Zöllner, H; Greinacher, A

    2014-06-01

    Heparin-induced thrombocytopenia (HIT) is an adverse drug reaction and prothrombotic disorder caused by immunization against platelet factor 4 (PF4) after complex formation with heparin or other polyanions. After antibody binding to PF4/heparin complexes, HIT antibodies are capable of intravascular platelet activation by cross-linking Fc gamma receptor IIa (FcγRIIa) on the platelet surface leading to a platelet count decrease and/or thrombosis. In contrast to most other immune-mediated disorders, the currently available laboratory tests for anti-PF4/heparin antibodies show a high sensitivity also for clinically irrelevant antibodies. This makes the diagnosis of HIT challenging and bears the risk to substantially overdiagnose HIT. The strength of the antigen assays for HIT is in ruling out HIT when the test is negative. Functional assays have a higher specificity for clinically relevant antibodies, but they are restricted to specialized laboratories. Currently, a Bayesian approach combining the clinical likelihood estimation for HIT with laboratory tests is the most appropriate approach to diagnose HIT. In this review, we give an overview on currently available diagnostic procedures and discuss their limitations. © 2014 John Wiley & Sons Ltd.

  10. Hybrid Calcium Phosphate-Polymeric Micelles Incorporating Gadolinium Chelates for Imaging-Guided Gadolinium Neutron Capture Tumor Therapy.

    Science.gov (United States)

    Mi, Peng; Dewi, Novriana; Yanagie, Hironobu; Kokuryo, Daisuke; Suzuki, Minoru; Sakurai, Yoshinori; Li, Yanmin; Aoki, Ichio; Ono, Koji; Takahashi, Hiroyuki; Cabral, Horacio; Nishiyama, Nobuhiro; Kataoka, Kazunori

    2015-06-23

    Gadolinium (Gd) chelates-loaded nanocarriers have high potential for achieving magnetic resonance imaging (MRI)-guided Gd neutron capture therapy (GdNCT) of tumors. Herein, we developed calcium phosphate micelles hybridized with PEG-polyanion block copolymers, and incorporated with the clinical MRI contrast agent Gd-diethylenetriaminepentaacetic acid (Gd-DTPA/CaP). The Gd-DTPA/CaP were nontoxic to cancer cells at the concentration of 100 μM based on Gd-DTPA, while over 50% of the cancer cells were killed by thermal neutron irradiation at this concentration. Moreover, the Gd-DTPA/CaP showed a dramatically increased accumulation of Gd-DTPA in tumors, leading to the selective contrast enhancement of tumor tissues for precise tumor location by MRI. The enhanced tumor-to-blood distribution ratio of Gd-DTPA/CaP resulted in the effective suppression of tumor growth without loss of body weight, indicating the potential of Gd-DTPA/CaP for safe cancer treatment.

  11. Engineering polyelectrolyte multilayer structure at the nanometer length scale by tuning polymer solution conformation.

    Science.gov (United States)

    Boddohi, Soheil; Killingsworth, Christopher; Kipper, Matt

    2008-03-01

    Chitosan (a weak polycation) and heparin (a strong polyanion) are used to make polyelectrolyte multilayers (PEM). PEM thickness and composition are determined as a function of solution pH (4.6 to 5.8) and ionic strength (0.1 to 0.5 M). Over this range, increasing pH increases the PEM thickness; however, the sensitivity to changes in pH is a strong function of ionic strength. The PEM thickness data are correlated to the polymer conformation in solution. Polyelectrolyte conformation in solution is characterized by gel permeation chromatography (GPC). The highest sensitivity of PEM structure to pH is obtained at intermediate ionic strength. Different interactions govern the conformation and adsorption phenomena at low and high ionic strength, leading to reduced sensitivity to solution pH at extreme ionic strengths. The correspondence between PEM thickness and polymer solution conformation offers opportunities to tune polymer thin film structure at the nanometer length scale by controlling simple, reproducible processing conditions.

  12. Polyelectrolyte multilayer assembly as a function of pH and ionic strength using the polysaccharides chitosan and heparin.

    Science.gov (United States)

    Boddohi, Soheil; Killingsworth, Christopher E; Kipper, Matt J

    2008-07-01

    The goal of this work is to explore the effects of solution ionic strength and pH on polyelectrolyte multilayer (PEM) assembly, using biologically derived polysaccharides as the polyelectrolytes. We used the layer-by-layer (LBL) technique to assemble PEM of the polysaccharides heparin (a strong polyanion) and chitosan (a weak polycation) and characterized the sensitivity of the PEM composition and layer thickness to changes in processing parameters. Fourier-transform surface plasmon resonance (FT-SPR) and spectroscopic ellipsometry provided in situ and ex situ measurements of the PEM thickness, respectively. Vibrational spectroscopy and X-ray photoelectron spectroscopy (XPS) provided details of the chemistry (i.e., composition, electrostatic interactions) of the PEM. We found that when PEM were assembled from 0.2 M buffer, the PEM thickness could be increased from less than 2 nm per bilayer to greater than 4 nm per bilayer by changing the solution pH; higher and lower ionic strength buffer solutions resulted in narrower ranges of accessible thickness. Molar composition of the PEM was not very sensitive to solution pH or ionic strength, but pH did affect the interactions between the sulfonates in heparin and amines in chitosan when PEM were assembled from 0.2 M buffer. Changes in the PEM thickness with pH and ionic strength can be interpreted through descriptions of the charge density and conformation of the polyelectrolyte chains in solution.

  13. The Non-Hemostatic Aspects of Transfused Platelets

    Science.gov (United States)

    Sut, Caroline; Tariket, Sofiane; Aubron, Cécile; Aloui, Chaker; Hamzeh-Cognasse, Hind; Berthelot, Philippe; Laradi, Sandrine; Greinacher, Andreas; Garraud, Olivier; Cognasse, Fabrice

    2018-01-01

    Platelets transfusion is a safe process, but during or after the process, the recipient may experience an adverse reaction and occasionally a serious adverse reaction (SAR). In this review, we focus on the inflammatory potential of platelet components (PCs) and their involvement in SARs. Recent evidence has highlighted a central role for platelets in the host inflammatory and immune responses. Blood platelets are involved in inflammation and various other aspects of innate immunity through the release of a plethora of immunomodulatory cytokines, chemokines, and associated molecules, collectively termed biological response modifiers that behave like ligands for endothelial and leukocyte receptors and for platelets themselves. The involvement of PCs in SARs—particularly on a critically ill patient’s context—could be related, at least in part, to the inflammatory functions of platelets, acquired during storage lesions. Moreover, we focus on causal link between platelet activation and immune-mediated disorders (transfusion-associated immunomodulation, platelets, polyanions, and bacterial defense and alloimmunization). This is linked to the platelets’ propensity to be activated even in the absence of deliberate stimuli and to the occurrence of time-dependent storage lesions. PMID:29536007

  14. Activity and lifetime of urease immobilized using layer-by-layer nano self-assembly on silicon microchannels.

    Science.gov (United States)

    Forrest, Scott R; Elmore, Bill B; Palmer, James D

    2005-01-01

    Urease has been immobilized and layered onto the walls of manufactured silicon microchannels. Enzyme immobilization was performed using layer-by-layer nano self-assembly. Alternating layers of oppositely charged polyelectrolytes, with enzyme layers "encased" between them, were deposited onto the walls of the silicon microchannels. The polycations used were polyethylenimine (PEI), polydiallyldimethylammonium (PDDA), and polyallylamine (PAH). The polyanions used were polystyrenesulfonate (PSS) and polyvinylsulfate (PVS). The activity of the immobilized enzyme was tested by pumping a 1 g/L urea solution through the microchannels at various flow rates. Effluent concentration was measured using an ultraviolet/visible spectrometer by monitoring the absorbance of a pH sensitive dye. The architecture of PEI/PSS/PEI/urease/PEI with single and multiple layers of enzyme demonstrated superior performance over the PDDA and PAH architectures. The precursor layer of PEI/PSS demonstrably improved the performance of the reactor. Conversion rates of 70% were achieved at a residence time of 26 s, on d 1 of operation, and >50% at 51 s, on d 15 with a six-layer PEI/urease architecture.

  15. Enzymatic studies on the metabolism of the tetrahydrofurfuryl mercaptan moiety of thiamine tetrahydrofurfuryl disulfide, 2

    International Nuclear Information System (INIS)

    Fujita, Takeshi; Suzuoki, Ziro; Kozuka, Seizi; Oae, Shigeru.

    1973-01-01

    The second step in the enzymatic process responsible for the novel metabolic pathway of foreign mercaptans leading to methylsulfonyl metabolites was shown to be sulfoxidation, subsequent to S-methylation. By using [ 35 S] methyl tetrahydrofurfuryl sulfide (MTFS) and [ 35 S] methyl tetrahydrofurfuryl sulfoxide (MTFSO) as substrates, the occurrence and involvement of both sulfide and sulfoxide oxygenases were demonstrated in rat liver microsomes. Both activities required reduced nicotinamide adenine dinucleotide phosphate (NADPH) and O 2 . The reaction products were isolated and identified as MTFSO and its sulfone, respectively. The apparent Michaelis constants were 6.7x10 -4 M for MTFS and 9.1x10 -15 M for NADPH with sulfide oxygenase and 5.6x10 -3 M for MTFSO and 5.0x10 -5 M for NADPH with sulfoxide oxygenase, respectively. P-chloromercuribenzoate, P-chloromercuribenzenesulfonate, HgCl 2 , and menadione strongly inhibited both oxygenases. Polyanions, such as inorganic phosphate, pyrophosphate, sulfate, and ATP stimulated both enzyme activities, especially that of sulfoxide oxygenase. One atom of 18 O 2 was incorporated into the products in both enzyme reactions. No appreciable incorporation was observed from H 2 18 O. These results indicate that both enzyme systems are typical monooxygenases. (auth.)

  16. L-Arginine ethylester enhances in vitro amplification of PrP(Sc) in macaques with atypical L-type bovine spongiform encephalopathy and enables presymptomatic detection of PrP(Sc) in the bodily fluids.

    Science.gov (United States)

    Murayama, Y; Ono, F; Shimozaki, N; Shibata, H

    2016-02-12

    Protease-resistant, misfolded isoforms (PrP(Sc)) of a normal cellular prion protein (PrP(C)) in the bodily fluids, including blood, urine, and saliva, are expected to be useful diagnostic markers of prion diseases, and nonhuman primate models are suited for performing valid diagnostic tests for human Creutzfeldt-Jakob disease (CJD). We developed an effective amplification method for PrP(Sc) derived from macaques infected with the atypical L-type bovine spongiform encephalopathy (L-BSE) prion by using mouse brain homogenate as a substrate in the presence of polyanions and L-arginine ethylester. This method was highly sensitive and detected PrP(Sc) in infected brain homogenate diluted up to 10(10) by sequential amplification. This method in combination with PrP(Sc) precipitation by sodium phosphotungstic acid is capable of amplifying very small amounts of PrP(Sc) contained in the cerebrospinal fluid (CSF), saliva, urine, and plasma of macaques that have been intracerebrally inoculated with the L-BSE prion. Furthermore, PrP(Sc) was detectable in the saliva or urine samples as well as CSF samples obtained at the preclinical phases of the disease. Thus, our novel method may be useful for furthering the understanding of bodily fluid leakage of PrP(Sc) in nonhuman primate models. Copyright © 2016 Elsevier Inc. All rights reserved.

  17. NAA-modified DNA oligonucleotides with zwitterionic backbones: stereoselective synthesis of A-T phosphoramidite building blocks.

    Science.gov (United States)

    Schmidtgall, Boris; Höbartner, Claudia; Ducho, Christian

    2015-01-01

    Modifications of the nucleic acid backbone are essential for the development of oligonucleotide-derived bioactive agents. The NAA-modification represents a novel artificial internucleotide linkage which enables the site-specific introduction of positive charges into the otherwise polyanionic backbone of DNA oligonucleotides. Following initial studies with the introduction of the NAA-linkage at T-T sites, it is now envisioned to prepare NAA-modified oligonucleotides bearing the modification at X-T motifs (X = A, C, G). We have therefore developed the efficient and stereoselective synthesis of NAA-linked 'dimeric' A-T phosphoramidite building blocks for automated DNA synthesis. Both the (S)- and the (R)-configured NAA-motifs were constructed with high diastereoselectivities to furnish two different phosphoramidite reagents, which were employed for the solid phase-supported automated synthesis of two NAA-modified DNA oligonucleotides. This represents a significant step to further establish the NAA-linkage as a useful addition to the existing 'toolbox' of backbone modifications for the design of bioactive oligonucleotide analogues.

  18. Mutation directional selection sheds light on prion pathogenesis

    International Nuclear Information System (INIS)

    Shen, Liang; Ji, Hong-Fang

    2011-01-01

    Highlights: → Most pathogenic mutations possess strong directional selection, i.e., enhancing hydrophobicity or decreasing negative and increasing positive charge. → Mutation-induced changes may strengthen the interactions between PrP and facilitating factors. → The findings also have significant implications for exploring potential regions involved in the conformational transition from PrP C to PrP Sc . -- Abstract: As mutations in the PRNP gene account for human hereditary prion diseases (PrDs), it is crucial to elucidating how these mutations affect the central pathogenic conformational transition of normal cellular prion protein (PrP C ) to abnormal scrapie isoform (PrP Sc ). Many studies proposed that these pathogenic mutations may make PrP more susceptible to conformational change through altering its structure stability. By evaluating the most recent observations regarding pathogenic mutations, it was found that the pathogenic mutations do not exert a uniform effect on the thermodynamic stability of the human PrP's structure. Through analyzing the reported PrDs-related mutations, we found that 25 out of 27 mutations possess strong directional selection, i.e., enhancing hydrophobicity or decreasing negative and increasing positive charge. Based on the triggering role reported by previous studies of facilitating factors in PrP C conversion, e.g., lipid and polyanion, we proposed that the mutation-induced changes may strengthen the interaction between PrP and facilitating factors, which will accelerate PrP conversion and cause PrDs.

  19. Preparation and ion sensing property of the self-assembled microgels by QCM

    Directory of Open Access Journals (Sweden)

    Cao Zheng

    2018-03-01

    Full Text Available The polyanion polystyrene sulfonate (PSS, the polycation poly (allylamine hydrochloride (PAH, and the anionic poly (N-isopropylacrylamide-co-acrylic acid [P(NIPAM-co-AA] microgels were self-assembled onto the polyethylene imine (PEI adsorbed gold surfaces of quartz crystal microbalance (QCM because of the electrostatic attractions. The interactions of various metal particles including Ca2+, Bi3+, Cu2+, Zn2+, Ni2+, Sn2+, Co2+, and Cd2+ with the obtained PEI/PSS/PAH/microgel layer in aqueous solutions were evaluated by QCM. The PEI/PSS/PAH/Microgel covered QCM sensor demonstrates the lowest detection limit of 0.1 ppm in aqueous solutions and the obviously linear connection between the frequency response and Ni2+ concentration from 0.1 to 20 ppm, which is due to the complexation of Ni2+ with the carboxyl groups of microgels. Atomic force microscopy (AFM was used to reveal the morphology and stability of the self-assembled polyelectrolyte/microgel layer before and after adsorbing heavy metal ions. These self-assembled materials of polyelectrolyte/microgel layer will be helpful for manufacturing ion-selective materials for separation and identification purposes.

  20. Naked eye detection of infertility based on sperm protamine-induced aggregation of heparin gold nanoparticles.

    Science.gov (United States)

    Vidya, Raj; Saji, Alex

    2018-05-01

    The development of an easy to use, one-pot, environmentally friendly, non-invasive and label-free colorimetric probe for the determination of semen protamines, the biochemical marker of male fertility, using heparin gold nanoparticles (HAuNPs) is presented. The affinity of HAuNPs for protamines was due to the electrostatic interactions between polycationic protamine and polyanionic heparin. The binding of HAuNPs to protamine was characterized by variation in the plasmon absorption spectra followed by a visibly observable colour change of the solution from red to blue. We observed a red shift in the plasmon peak and the method exhibited linearity in the range of 10-70 ng/mL with a detection limit of 5 ng/mL, which is much lower than that reported for colorimetric sensors of protamine. The colour change and the variation in the absorbance of HAuNPs were highly specific for protamines in the presence of different interfering compounds and the method was successfully applied for determining protamine in real samples of semen and serum. Rather than a quantitative estimation, it seems that the method provides a quick screening between a large array of positive and negative samples and, moreover, it maintains the privacy of the user. The method appears to be simple and would be very useful in third-world countries where high-tech diagnostic aids are inaccessible to the majority of the population. Graphical Abstract Heparin gold nanoparticles aided visual detection of infertility.

  1. An oxygen-insensitive hydrogen evolution catalyst coated by a molybdenum-based layer for overall water splitting

    Energy Technology Data Exchange (ETDEWEB)

    Garcia-Esparza, Angel T.; Shinagawa, Tatsuya; Ould-Chikh, Samy; Qureshi, Muhammad; Peng, Xuyuan; Takanabe, Kazuhiro [KAUST Catalysis Center (KCC) and Physical Science and Engineering Division - PSE, King Abdullah University of Science and Technology (KAUST), Thuwal (Saudi Arabia); Wei, Nini; Anjum, Dalaver H. [Advanced Nanofabrication, Imaging and Characterization Core Lab, King Abdullah University of Science and Technology (KAUST), Thuwal (Saudi Arabia); Clo, Alain [Research Computing, King Abdullah University of Science and Technology (KAUST), Thuwal (Saudi Arabia); Weng, Tsu-Chien [Center for High Pressure Science and Technology Advanced Research, Shanghai (China); Nordlund, Dennis; Sokaras, Dimosthenis [Stanford Synchrotron Radiation Lightsource, Menlo Park, CA (United States); Kubota, Jun [Department of Chemical Engineering, Fukuoka University (Japan); Domen, Kazunari [Department of Chemical System Engineering, School of Engineering, The University of Tokyo (Japan)

    2017-05-15

    For overall water-splitting systems, it is essential to establish O{sub 2}-insensitive cathodes that allow cogeneration of H{sub 2} and O{sub 2}. An acid-tolerant electrocatalyst is described, which employs a Mo-coating on a metal surface to achieve selective H{sub 2} evolution in the presence of O{sub 2}. In operando X-ray absorption spectroscopy identified reduced Pt covered with an amorphous molybdenum oxyhydroxide hydrate with a local structural order composed of polyanionic trimeric units of molybdenum(IV). The Mo layer likely hinders O{sub 2} gas permeation, impeding contact with active Pt. Photocatalytic overall water splitting proceeded using MoO{sub x}/Pt/SrTiO{sub 3} with inhibited water formation from H{sub 2} and O{sub 2}, which is the prevailing back reaction on the bare Pt/SrTiO{sub 3} photocatalyst. The Mo coating was stable in acidic media for multiple hours of overall water splitting by membraneless electrolysis and photocatalysis. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  2. Equiatomic indides REIrIn (RE=La, Pr, Nd, Er-Yb). Crystal and electronic structure

    Energy Technology Data Exchange (ETDEWEB)

    Zaremba, Nazar [Ivan Franko National Univ. of Lviv (Ukraine). Dept. of Inorganic Chemistry; Technische Univ. Muenchen, Garching (Germany). Fakultaet fuer Chemie; Muts, Ihor; Zaremba, Vasyl [Ivan Franko National Univ. of Lviv (Ukraine). Dept. of Inorganic Chemistry; Hlukhyy, Viktor [Technische Univ. Muenchen, Garching (Germany). Fakultaet fuer Chemie; Stein, Sebastian; Rodewald, Ute C.; Poettgen, Rainer [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie; Pavlyuk, Volodymyr [Ivan Franko National Univ. of Lviv (Ukraine). Dept. of Inorganic Chemistry; Czestochowa Jan Dlugosz Univ., Czestochowa (Poland). Inst. of Chemistry, Environmental Protection and Biotechnology

    2017-10-01

    The equiatomic rare earth iridium indides REIrIn (RE=La, Pr, Nd, Er-Yb) were synthesized by reaction of the elements in induction or muffle furnaces and were characterized through X-ray powder patterns. The structures of LaIr{sub 0.86}In{sub 1.14}, PrIr{sub 0.89}In{sub 1.11}, NdIr{sub 0.94}In{sub 1.06}, ErIrIn (all ZrNiAl type, P anti 62m), and YbIrIn (TiNiSi type, Pnma) were refined from single crystal X-ray diffractometer data. Refinements of the occupancy parameters revealed small degrees of solid solutions with indium substitution on the iridium sites. Chemical bonding analyses and electronic structure calculations indicate the dominance of metallic bonding in addition to partial ionic interactions between the cations and polyanions, as well as covalent contributions between the indium and iridium atoms.

  3. Proton-binding capacity of Staphylococcus aureus wall teichoic acid and its role in controlling autolysin activity.

    Directory of Open Access Journals (Sweden)

    Raja Biswas

    Full Text Available Wall teichoic acid (WTA or related polyanionic cell wall glycopolymers are produced by most gram-positive bacterial species and have been implicated in various cellular functions. WTA and the proton gradient across bacterial membranes are known to control the activity of autolysins but the molecular details of these interactions are poorly understood. We demonstrate that WTA contributes substantially to the proton-binding capacity of Staphylococcus aureus cell walls and controls autolysis largely via the major autolysin AtlA whose activity is known to decline at acidic pH values. Compounds that increase or decrease the activity of the respiratory chain, a main source of protons in the cell wall, modulated autolysis rates in WTA-producing cells but did not affect the augmented autolytic activity observed in a WTA-deficient mutant. We propose that WTA represents a cation-exchanger like mesh in the gram-positive cell envelopes that is required for creating a locally acidified milieu to govern the pH-dependent activity of autolysins.

  4. Human mesenchymal stem cell osteoblast differentiation, ECM deposition, and biomineralization on PAH/PAA polyelectrolyte multilayers.

    Science.gov (United States)

    Pattabhi, Sudhakara Rao; Lehaf, Ali M; Schlenoff, Joseph B; Keller, Thomas C S

    2015-05-01

    Polyelectrolyte multilayer (PEMU) coatings built layer by layer with alternating pairs of polyelectrolytes can be tuned to improve cell interactions with surfaces and may be useful as biocompatible coatings to improve fixation between implants and tissues. Here, we show that human mesenchymal stromal cells (hMSCs) induced with bone differentiation medium (BDM) to become osteoblasts biomineralize crosslinked PEMUs built with the polycation poly(allylamine hydrochloride) (PAH) and the polyanion poly(acrylic acid) (PAA). Degrees of hMSC osteoblast differentiation and surface biomineralization on the smooth PAH-terminated PEMUs (PAH-PEMUs) and microstructured PAA-terminated PEMUs (PAA-PEMUs) reflect differences in cell-deposited extracellular matrix (ECM). BDM-induced hMSCs expressed higher levels of the early osteoblast differentiation marker alkaline phosphatase and collagen 1 (COL1) sooner on PAA-PEMUs than on PAH-PEMUs. Cells on both types of PEMUs proceeded to express the later stage osteoblast differentiation marker bone sialoprotein (BSP), but the BDM-induced cells organized a more amorphous Collagen I and denser BSP localization on PAA-PEMUs than on PAH-PEMUs. These ECM properties correlated with greater biomineralization on the PAA-PEMUs than on PAH-PEMUs. Together, these results confirm the suitability of PAH/PAA PEMUs as a substrate for hMSC osteogenesis and highlight the importance of substrate effects on ECM organization and BSP presentation on biomineralization. © 2014 Wiley Periodicals, Inc.

  5. Ag-ligand modified tungstovandates and their efficient catalysis degradation properties for methylene blue

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Ran; Zhang, Huixia; Liu, Yunping; Wang, Xiaoxiao; Han, Zhangang, E-mail: hanzg116@126.com

    2017-02-15

    Two polytungstovandates [Ag(mbpy){sub 2}][Ag{sub 2}(mbpy){sub 3}][VW{sub 5}O{sub 19}]·H{sub 2}O (1) and [Ag(mbpy)]{sub 2}[Ag(mbpy){sub 2}]{sub 4}[VW{sub 12}O{sub 40}] (2) (mbpy =4,4′-dimethyl-2,2′-bipyridyl), had been hydrothermally synthesized and characterized by IR, TG, and single-crystal X-ray diffraction techniques. Single-crystal structural analysis revealed that the polyanionic clusters in two compounds are different: Lindqvist-type in 1 and α-Keggin-type in 2, respectively, while the cationic moieties in them are Ag-mbpy units. The experiments showed that this kind of hybrid crystal materials possesses more efficiently catalytic performance for the degradation of organic dye methylene blue (MB) in water solution under the UV irradiation. The significant degradation rate of MB can reach 89.9%, 94.9% by crystals 1 and 2 (40 mg) in the course of about 5 min. - Graphical abstract: Two Ag-ligand modified polytungstovandates had been synthesized and characterized, which were active in the catalytic degradation of organic dye methylene blue under the UV irradiation. - Highlights: • Two Ag-ligand modified tungstovandates were synthesized and characterized. • Weak interactions play important roles in constructing crystal frameworks. • Compounds are active to catalyze the degradation of methylene blue.

  6. From fundamental supramolecular chemistry to self-assembled nanomaterials and medicines and back again - how Sam inspired SAMul.

    Science.gov (United States)

    Smith, David K

    2018-05-08

    This feature article provides a personal insight into the research from my group over the past 10 years. In particular, the article explains how, inspired in 2005 by meeting my now-husband, Sam, who had cystic fibrosis, and who in 2011 went on to have a double lung transplant, I took an active decision to follow a more applied approach to some of our research, attempting to use fundamental supramolecular chemistry to address problems of medical interest. In particular, our strategy uses self-assembly to fabricate biologically-active nanosystems from simple low-molecular-weight building blocks. These systems can bind biological polyanions in highly competitive conditions, allowing us to approach applications in gene delivery and coagulation control. In the process, however, we have also developed new fundamental principles such as self-assembled multivalency (SAMul), temporary 'on-off' multivalency, and adaptive/shape-persistent multivalent binding. By targeting materials with applications in drug formulation and tissue engineering, we have discovered novel self-assembling low-molecular-weight hydrogelators based on the industrially-relevant dibenzylidenesorbitol framework and developed innovative approaches to spatially-resolved gels and functional multicomponent hybrid hydrogels. In this way, taking an application-led approach to research has also delivered significant academic value and conceptual advances. Furthermore, beginning to translate fundamental supramolecular chemistry into real-world applications, starts to demonstrate the power of this approach, and its potential to transform the world around us for the better.

  7. Characterization and Optimization of Bioflocculant Exopolysaccharide Production by Cyanobacteria Nostoc sp. BTA97 and Anabaena sp. BTA990 in Culture Conditions.

    Science.gov (United States)

    Tiwari, Onkar Nath; Khangembam, Romi; Shamjetshabam, Minerva; Sharma, Aribam Subhalaxmi; Oinam, Gunapati; Brand, Jerry J

    2015-08-01

    Bioflocculant exopolysaccharide (EPS) production by 40 cyanobacterial strains during their photoautotrophic growth was investigated. Highest levels of EPS were produced by Nostoc sp. BTA97 and Anabaena sp. BTA990. EPS production was maximum during stationary growth phase, when nitrogenase activity was very low. Maximum EPS production occurred at pH 8.0 in the absence of any combined nitrogen source. The cyanobacterial EPS consisted of soluble protein and polysaccharide that included substantial amounts of neutral sugars and uronic acid. The EPS isolated from Anabaena sp. BTA990 and Nostoc sp. BTA97 demonstrated high flocculation capacity. There was a positive correlation between uronic acid content and flocculation activity. The flocculant bound a cationic dye, Alcian Blue, indicating it to be polyanionic. The 16S rRNA gene sequences for Nostoc sp. BTA97 and Anabaena sp. BTA990 were deposited at NCBI GenBank, and accession numbers were obtained as KJ830951 and KJ830948, respectively. The results of these experiments indicate that strains Anabaena sp. BTA990 and Nostoc sp. BTA97 are good candidates for the commercial production of EPS and might be utilized in industrial applications as an alternative to synthetic and abiotic flocculants.

  8. Sodium intercalation in the phosphosulfate cathode NaFe2(PO4)(SO4)2

    Science.gov (United States)

    Ben Yahia, Hamdi; Essehli, Rachid; Amin, Ruhul; Boulahya, Khalid; Okumura, Toyoki; Belharouak, Ilias

    2018-04-01

    The compound NaFe2(PO4)(SO4)2 is successfully synthesized via a solid state reaction route and its crystal structure is determined using powder X-ray diffraction data. NaFe2(PO4)(SO4)2 phase is also characterized by cyclic voltammetry, galvanostatic cycling and electrochemical impedance spectroscopy. NaFe2(PO4)(SO4)2 crystallizes with the well-known NASICON-type structure. SAED and HRTEM experiments confirm the structural model, and no ordering between the PO4-3 and SO4-2 polyanions is detected. The electrochemical tests indicate that NaFe2(PO4)(SO4)2 is a 3 V sodium intercalating cathode. The electrical conductivity is relatively low (2.2 × 10-6 Scm-1 at 200 °C) and the obtained activation energy is ∼0.60eV. The GITT experiments indicate that the diffusivity values are in the range of 10-11-10-12 cm2/s within the measured sodium concentrations.

  9. Synthesis and structure of Sr{sub 2}Pd{sub 2}In and Sr{sub 2}Pt{sub 2}In

    Energy Technology Data Exchange (ETDEWEB)

    Muts, I. [Inst. fuer Anorganische und Analytische Chemie, Univ. Muenster (Germany); Inorganic Chemistry Dept., Ivan Franko National Univ. of Lviv (Ukraine); Nilges, T.; Rodewald, U.C.; Poettgen, R. [Inst. fuer Anorganische und Analytische Chemie, Univ. Muenster (Germany); Zaremba, V.I. [Inorganic Chemistry Dept., Ivan Franko National Univ. of Lviv (Ukraine)

    2007-12-15

    The new intermetallic compounds Sr{sub 2}Pd{sub 2}In and Sr{sub 2}Pt{sub 2}In were synthesized from the elements in sealed tantalum tubes in a water-cooled sample chamber of an induction furnace. Both indides crystallize with the HT-Pr{sub 2}Co{sub 2}Al-type structure: C2/c, a = 1048.7(2), b = 603.5(2), c = 830.6(1) pm. {beta} = 103.68(2) , wR2 = 0.0492, 743 F{sup 2} values for Sr{sub 2}Pd{sub 2}In; a = 1026.8(2), b = 599.0(1), c = 830.3(2) pm, {beta} = 103.17(1) , wR2 = 0.0666, 885 F{sup 2} values for Sr{sub 2}Pt{sub 2}In with 25 variables per refinement. The shortest interatomic distances occur for the Pd-In (Pt-In) and Pd-Pd (Pt-Pt) contacts. The strontium atoms are embedded in complex three-dimensional polyanionic networks of compositions [Pd{sub 2}In] and [Pt{sub 2}In]. (orig.)

  10. A Cadmium Anionic 1-D Coordination Polymer {[Cd(H2O6][Cd2(atr2(μ2-btc2(H2O4] 2H2O}n within a 3-D Supramolecular Charge-Assisted Hydrogen-Bonded and π-Stacking Network

    Directory of Open Access Journals (Sweden)

    Anas Tahli

    2016-03-01

    Full Text Available The hydrothermal reaction of 4,4′-bis(1,2,4-triazol-4-yl (btr and benzene-1,3,5-tricarboxylic acid (H3btc with Cd(OAc2·2H2O at 125 °C in situ forms 4-amino-1,2,4-triazole (atr from btr, which crystallizes to a mixed-ligand, poly-anionic chain of [Cd2(atr2(µ2-btc2(H2O4]2–. Together with a hexaaquacadmium(II cation and water molecules the anionic coordination-polymeric forms a 3-D supramolecular network of hexaaquacadmium(II-catena-[bis(4-amino-1,2,4-triazoletetraaquabis(benzene-1,3,5-tricarboxylatodicadmate(II] dihydrate, 1-D-{[Cd(H2O6][Cd2(atr2(µ2-btc2(H2O4] 2H2O}n which is based on hydrogen bonds (in part charge-assisted and π–π interactions.

  11. Imprinting of metal receptors into multilayer polyelectrolyte films: fabrication and applications in marine antifouling† †Electronic supplementary information (ESI) available: FTIR, NMR spectra of synthesized polymers, XPS spectra and AFM images of non-cross linked and cross linked LBLA and LBLB films, UV-Visible absorption spectra of copper complexation with PAH-His, QCM data of LBLA and LBLB films and stability of the films are provided in the electronic supplementary information. See DOI: 10.1039/c4sc02367f Click here for additional data file.

    Science.gov (United States)

    Puniredd, Sreenivasa Reddy; Go, Dewi Pitrasari; Zhu, Xiaoying; Guo, Shifeng; Ming Teo, Serena Lay; Chen Lee, Serina Siew

    2015-01-01

    Polymeric films constructed using the layer-by-layer (LbL) fabrication process were employed as a platform for metal ion immobilization and applied as a marine antifouling coating. The novel Cu2+ ion imprinting process described is based on the use of metal ion templates and LbL multilayer covalent cross-linking. Custom synthesized, peptide mimicking polycations composed of histidine grafted poly(allylamine) (PAH) to bind metal ions, and methyl ester containing polyanions for convenient cross-linking were used in the fabrication process. Two methods of LbL film formation have been investigated using alternate polyelectrolyte deposition namely non-imprinted LbLA, and imprinted LbLB. Both LbL films were cross linked at mild temperature to yield covalent bridging of the layers for improved stability in a sea water environment. A comparative study of the non-imprinted LbLA films and imprinted LbLB films for Cu2+ ion binding capacity, leaching rate and stability of the films was performed. The results reveal that the imprinted films possess enhanced affinity to retain metal ions due to the preorganization of imidazole bearing histidine receptors. As a result the binding capacity of the films for Cu2+ could be improved by seven fold. Antifouling properties of the resulting materials in a marine environment have been demonstrated against the settlement of barnacle larvae, indicating that controlled release of Cu ions was achieved. PMID:28966763

  12. Dynamic Contact Angle Analysis of Protein Adsorption on Polysaccharide Multilayer’s Films for Biomaterial Reendothelialization

    Directory of Open Access Journals (Sweden)

    Safiya Benni

    2014-01-01

    Full Text Available Atherosclerosis is a major cardiovascular disease. One of the side effects is restenosis. The aim of this work was to study the coating of stents by dextran derivates based polyelectrolyte’s multilayer (PEM films in order to increase endothelialization of injured arterial wall after stent implantation. Films were composed with diethylaminoethyl dextran (DEAE as polycation and dextran sulphate (DS as polyanion. One film was composed with 4 bilayers of (DEAE-DS4 and was labeled D−. The other film was the same as D− but with an added terminal layer of DEAE polycation: (DEAE-DS4-DEAE (labeled D+. The dynamic adsorption/desorption of proteins on the films were characterized by dynamic contact angle (DCA and atomic force microscopy (AFM. Human endothelial cell (HUVEC adhesion and proliferation were quantified and correlated to protein adsorption analyzed by DCA for fibronectin, vitronectin, and bovine serum albumin (BSA. Our results showed that the endothelial cell response was optimal for films composed of DS as external layer. Fibronectin was found to be the only protein to exhibit a reversible change in conformation after desorption test. This behavior was only observed for (DEAE-DS4 films. (DEAE-DS4 films could enhance HUVEC proliferation in agreement with fibronectin ability to easily change from conformation.

  13. Hyaluronic acid: a unique topical vehicle for the localized delivery of drugs to the skin.

    Science.gov (United States)

    Brown, M B; Jones, S A

    2005-05-01

    Hyaluronic acid (HA) is a naturally occurring polyanionic, polysaccharide that consists of N-acetyl-D-glucosamine and beta-glucoronic acid. It is present in the intercellular matrix of most vertebrate connective tissues especially skin where it has a protective, structure stabilizing and shock-absorbing role. The unique viscoelastic nature of HA along with its biocompatibility and non-immunogenicity has led to its use in a number of clinical applications, which include: the supplementation of joint fluid in arthritis; as a surgical aid in eye surgery; and to facilitate the healing and regeneration of surgical wounds. More recently, HA has been investigated as a drug delivery agent for various routes of administration, including ophthalmic, nasal, pulmonary, parenteral and topical. In fact, regulatory approval in the USA, Canada and Europe was granted recently for 3% diclofenac in 2.5% HA gel, Solaraze, for the topical treatment of actinic keratoses, which is the third most common skin complaint in the USA. The gel is well tolerated, safe and efficacious and provides an attractive, cost-effective alternative to cryoablation, curettage or dermabrasion, or treatment with 5-fluorouracil. The purpose of this review is to describe briefly the physical, chemical and biological properties of HA together with some details of its medical and pharmaceutical uses with emphasis on this more recent topical application.

  14. Water-Soluble Cellulose Derivatives Are Sustainable Additives for Biomimetic Calcium Phosphate Mineralization

    Directory of Open Access Journals (Sweden)

    Andreas Taubert

    2016-10-01

    Full Text Available The effect of cellulose-based polyelectrolytes on biomimetic calcium phosphate mineralization is described. Three cellulose derivatives, a polyanion, a polycation, and a polyzwitterion were used as additives. Scanning electron microscopy, X-ray diffraction, IR and Raman spectroscopy show that, depending on the composition of the starting solution, hydroxyapatite or brushite precipitates form. Infrared and Raman spectroscopy also show that significant amounts of nitrate ions are incorporated in the precipitates. Energy dispersive X-ray spectroscopy shows that the Ca/P ratio varies throughout the samples and resembles that of other bioinspired calcium phosphate hybrid materials. Elemental analysis shows that the carbon (i.e., polymer contents reach 10% in some samples, clearly illustrating the formation of a true hybrid material. Overall, the data indicate that a higher polymer concentration in the reaction mixture favors the formation of polymer-enriched materials, while lower polymer concentrations or high precursor concentrations favor the formation of products that are closely related to the control samples precipitated in the absence of polymer. The results thus highlight the potential of (water-soluble cellulose derivatives for the synthesis and design of bioinspired and bio-based hybrid materials.

  15. [Mo5VMo7VIO30(BPO4)2(O3P-Ph)6]5-: a phenyl-substituted molybdenum(V/VI) boro-phosphate polyoxometalate.

    Science.gov (United States)

    Sassoye, Capucine; Norton, Kieran; Sevov, Slavi C

    2003-03-10

    The title polyanion is the first hybrid borophosphate-phenylphosphonate polyoxometalate. It was structurally characterized as its imidazolium salt, (C(3)N(2)H(5))(5)[Mo(12)O(30)(BPO(4))(2)(O(3)P-Ph)(6)].H(2)O (monoclinic, P2(1)/c, a = 22.120(3) A, b = 13.042(2) A, and c = 32.632(4) A, beta = 101.293(3) degrees ), which was synthesized hydrothermally from imidazole, molybdenum oxide and metal, and boric, phosphoric, and phenylphosphonic acids. The anion is the second example of a new class of polyoxometalates that resemble Dawson anions but where the two pole caps of three edge-sharing MoO(6) octahedra in the latter are replaced by other units, in this case tetrahedral borate sharing corners with three phenylphosphonic groups, [(OB)(O(3)P-Ph)(3)]. The 12 molybdenum atoms forming the two equatorial belts of the cluster are of mixed-valence, five are Mo(V) and seven are Mo(VI), and the resulting five electrons are delocalized. Four of these electrons are paired according to the temperature dependence of the magnetic susceptibility. The new compound is soluble in a mixture of water and pyridine (in equal volumes) as well as in nitromethane, and the anions are intact in these solutions.

  16. Pseudoliquid behavior of heteropoly compound catalysts. Unusual pressure dependencies of the rate and selectivity for ethanol dehydration

    International Nuclear Information System (INIS)

    Misono, M.; Okuhara, T.; Ichiki, T.; Arai, T.; Kanda, Y.

    1987-01-01

    Heteropoly compounds arenow utilized as industrial catalysts for olefin hydration and aldehyde oxidation and as interesting cluster models of mixed oxide catalysts. Certain heteropoly acids, like H 3 PW 12 O 40 and H 3 PMo 12 O 40 , easily absorb a large amount of water, alchols, and ethers in the solid state, although their surface areas are very low. This is not adsorption in micropores; rather molecules are absorbed between the lattice polyanions, sometimes expanding the lattice. The expansion can be seen visually as well as by x-ray diffraction. The authors showed that in some cases catalytic reactions take place in this novel bulk phase. Presumably due to this behavior, very high catalytic activity and unique selectivity as well as unusual reactivity order have been observed. They called this state the pseudoliquid phase. However, in only one case was the amount of absorbed reactant measured under the working conditions. They report here unusual pressure dependencies of the rate and selectivity of ethanol dehydration over heteropoly compounds. The dependency can only be explained by the formation of a pseudoliquid phase, i.e., a phase where the amount of absorbed ethanol has changed as a function of ethanol pressure

  17. Chemical synthesis of guanosine diphosphate mannuronic acid (GDP-ManA) and its C-4-O-methyl and C-4-deoxy congeners.

    Science.gov (United States)

    Zhang, Qingju; Howell, P Lynne; Overkleeft, Herman S; Filippov, Dmitri V; van der Marel, Gijsbert A; Codée, Jeroen D C

    2017-10-10

    Described is the first synthesis of guanosine diphosphate mannuronic acid (GDP-ManA), the sugar donor used by algae and bacteria for the production of alginate, an anionic polysaccharide composed of β-d-mannuronic acid (ManA) and α-l-guluronic acid (GulA). Understanding the biosynthesis of these polyanionic polysaccharides on the molecular level, opens up avenues to use and modulate the biosynthesis machinery for biotechnological and therapeutic applications. The synthesis reported here delivers multi-milligram amounts of the GDP-ManA donor that can be used to study the polymerase (Alg8 in Pseudomonas aeruginosa) that generates the poly-ManA chain. Also reported is the assembly of two close analogues of GDP-ManA: the first bears a C-4-O-methyl group, while the second has been deoxygenated at this position. Both molecules may be used as "chain stoppers" in future enzymatic ManA polymerisation reactions. The crucial pyrophosphate linkage of the GDP-mannuronic acids has been constructed by the phosphorylation of the appropriate ManA-1-phosphates with a guanosine phosphoramidite. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. Effect of the ionic conductivity on the performance of polyelectrolyte-based supercapacitors

    Energy Technology Data Exchange (ETDEWEB)

    Wee, Grace; Srinivasan, Madhavi; Mhaisalkar, Subodh [School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Energy Research Institute rate at NTU (ERI rate at N), Research Techno Plaza, 5th Storey, 50 Nanyang Drive, Singapore 637553 (Singapore); Larsson, Oscar; Berggren, Magnus; Crispin, Xavier [Department of Science and Technology, Organic Electronics, Linkoeping University, SE-601 74 Norrkoeping (Sweden)

    2010-12-21

    In the emerging technology field of printed electronics, circuits are envisioned to be powered with printed energy sources, such as printed batteries and printed supercapacitors (SCs). For manufacturing and reliability issues, solid electrolytes are preferred instead of liquid electrolytes. Here, a solid-state, polyanionic proton conducting electrolyte, poly(styrenesulfonic acid) (PSS:H), is demonstrated for the first time as an effective ion conducting electrolyte medium in SCs with electrodes based on carbon nanotube (CNT) networks. The effect of the ionic conductivity in the PSS:H film of those SCs is studied at different levels of relative humidity (RH) with impedance spectroscopy, cyclic voltammetry, and galvanostatic charge-discharge techniques. High capacitance values (85 F g{sup -1} at 80% RH) are obtained for these SCs due to the extremely high effective electrode area of the CNTs and the enhanced ionic conductivity of the PSS:H film at increasing RH level. The charging dynamics are primarily limited by the ionic conductivity of the electrolyte rather than a poor contact between the electrolyte and the CNT electrodes. The use of polyelectrolytes in SCs provides high mechanical strength and flexibility, while maintaining a high capacitance value, enabling a new generation of printable solid-state charge storage devices. (Copyright copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  19. pH dependent green synthesis of gold nanoparticles by completely C6-carboxylated curdlan under high temperature and various pH conditions.

    Science.gov (United States)

    Qiu, Wen-Yi; Wang, Kai; Wang, Yao-Yao; Ding, Zhi-Chao; Wu, Li-Xia; Cai, Wu-Dan; Yan, Jing-Kun

    2018-01-01

    A C6-carboxylated curdlan (C6-Cc) obtained from 4-acetamido-TEMPO-mediated oxidation of curdlan was used both as a reducing and stabilizing agent for green synthesis of pH-responsive AuNPs, which was carried out by controlling the pH of the C6-Cc solution at a high temperature (100°C). C6-Cc presented a semi-flexible random coil chain in the aqueous medium at pH 5.5 and became more expanded and rigid in alkaline conditions (pH 7.1-12.0), though the primary chemical structure of C6-Cc was virtually unchanged with the pH variation. The AuNPs prepared with C6-Cc at various pHs were characterized by various instrumental measurements. The shapes and sizes of AuNPs were found to be strongly dependent on the pH of the C6-Cc solution. The C6-Cc-decorated AuNPs exhibited a more well-dispersed spherical morphology with smaller particle sizes under alkaline conditions (pH 7.1-12.0). Through this study, a facile, simple, and green method has been demonstrated for preparation of stimuli-sensitive AuNPs using biocompatible polyanionic polysaccharides. Copyright © 2017 Elsevier B.V. All rights reserved.

  20. Hematoxylin shortages: their causes and duration, and other dyes that can replace hemalum in routine hematoxylin and eosin staining.

    Science.gov (United States)

    Dapson, R; Horobin, R W; Kiernan, J

    2010-02-01

    The origins of repeated hematoxylin shortages are outlined. Lack of integration in the hematoxylin trade exacerbates the problems inherent in using a natural product. Separate corporations are engaged in tree growth and harvesting, dye extraction, processing of extracts to yield hematoxylin, and formulation and sale of hematoxylin staining solutions to the end users in biomedical laboratories. Hematoxylin has many uses in biological staining and no single dye can replace it for all applications. Probably, the most satisfactory substitutes for aluminum-hematoxylin (hemalum) are the ferric complexes of celestine blue (CI 51050; mordant blue 14) and eriochrome cyanine R (CI 43820; mordant blue 3, also known as chromoxane cyanine R and solochrome cyanine R). The iron-celestine blue complex is a cationic dye that binds to nucleic acids and other polyanions, such as those of cartilage matrix and mast cell granules. Complexes of iron with eriochrome cyanine R are anionic and give selective nuclear staining similar to that obtained with acidic hemalum solutions. Iron complexes of gallein (CI 45445; mordant violet 25), a hydroxyxanthene dye, can replace iron-hematoxylin in formulations for staining nuclei, myelin, and protozoa.

  1. Influence of serum percentage on the behavior of Wharton's jelly mesenchymal stem cells in culture.

    Science.gov (United States)

    Harmouch, C; El-Omar, R; Labrude, P; Decot, V; Menu, P; Kerdjoudj, H

    2013-01-01

    Mesenchymal stem cells (MSCs) are multipotent cells able to differentiate into several lineages with valuable applications in regenerative medicine. MSCs differentiation is highly dependent on physicochemical properties of the culture substrate, cell density and on culture medium composition. In this study, we assessed the influence of fetal bovine serum (FBS) level on Wharton's jelly (WJ)-MSCs behavior seeded on polyelectrolyte multilayer films (PEMF) made of four bilayers of poly-allylamine hydrochloride (PAH) as polycation and poly-styrene sulfonate (PSS) as polyanion. MSCs isolated from WJ by explants method were amplified until the third passage. Their phenotypic characterization was performed by flow cytometry analyses. MSCs were seeded on PEMF, in Endothelial growth medium-2 (EGM-2) supplemented by either 5% or 2% FBS. Cell's behavior was monitored for 20 days by optical microscopy and immunofluorescence. Until 2 weeks on glass slides, no difference was observed whatever the FBS percentage. Then with 5% FBS, MSCs formed three-dimensional spheroids on PSS/PAH after 20 days of culture with a nuclear aggregate. Whereas, with 2% FBS, these spheroids did not appear and cells grown in 2D conserved the fibroblast-like morphology. The decrease of FBS percentage from 5% to 2% avoids 3D cell spheroids formation on PAH/PSS. Such results could guide bioengineering towards building 2D structures like cell layers or 3D structures by increasing the osteogenic or chondrogenic differentiation potential of MSCs.

  2. Characterization of soft-combustion-derived NASICON-type Li2Co2(MoO4)3 for lithium batteries

    International Nuclear Information System (INIS)

    Prabaharan, S.R.S.; Ramesh, S.; Michael, M.S.; Begam, K.M.

    2004-01-01

    This work describes the synthesis of a new polyanion material, Li 2 Co 2 (MoO 4 ) 3 , belonging to the NASICON family. A low-temperature soft-combustion method using glycine as a soft-combustion fuel was adopted to obtain single-phase powders of the new material at a temperature as low as 300 deg. C. Li 2 Co 2 (MoO 4 ) 3 was found to crystallize in an orthorhombic structure (space group Pmmm) with lattice parameters a = 17.584(7) A, b 10.464(4) A and c = 5.102(9) A. The electronic state of each element present in the new material was confirmed by X-ray photoelectron spectroscopic analysis. The powders were analyzed using inductively coupled plasma emission spectroscopy. The microstructural analysis revealed that the particles (5-10 μm) have a rather columnar shape. The electrochemistry redox behavior of the new material was studied, for the first time, and the material as positive electrode was found to exhibit topotactic Li + extraction/insertion in lithium-containing test cells

  3. Crystal structure, hydrogen bonding, and sup 8 sup 1 Br NQR of low-temperature phase of 4-aminopyridinium tetrabromoantimonate (3)

    CERN Document Server

    Hashimoto, M; Fuess, H; Svoboda, I; Ehrenberg, H

    2003-01-01

    The crystal structure of the low-temperature phase (LTP) of the title compound was determined at 220 K (monoclinic, P2 sub 1 sub / sub c). The 4-aminopyridinium cations (4-NH sub 2 C sub 5 H sub 4 NH sup +) were found to be ordered in LTP, while being severely disordered in the room-temperature phase (monoclinic, C2/c). The tetrabromoantimonate anions (SbBr sub 4 sup -) were incorporated into the infinite polyanion chains of irregular SbBr sub 6 octahedra with two-edges sharing. The trans-Br-Sb-Br moiety in the SbBr sub 4 sup - anion was approximately symmetric differing from the asymmetric Br-Sb centre dot centre dot centre dot Br moiety found in LTP of pyridinium tetrabromoantimonate (3). The N-H moieties in both of the pyridine ring and the amino (-NH sub 2) group participate in the formation of N-H centre dot centre dot centre dot Br hydrogen bonds. It was shown that the sup 8 sup 1 Br NQR spectrum of LTP is closely related to the anion structure and the hydrogen bonds. The distinctive anion structures, a...

  4. The targeted transduction of MMP-overexpressing tumor cells by ACPP-HPMA copolymer-coated adenovirus conjugates.

    Directory of Open Access Journals (Sweden)

    Shuhua Li

    Full Text Available We have designed and tested a new way to selectively deliver HPMA polymer-coated adenovirus type 5 (Ad5 particles into matrix metalloproteinase (MMP-overexpressing tumor cells. An activatable cell penetrating peptide (ACPP was designed and attached to the reactive 4-nitrophenoxy groups of HPMA polymers by the C-terminal amino acid (asparagine, N. ACPPs are activatable cell penetrating peptides (CPPs with a linker between polycationic and polyanionic domains, and MMP-mediated cleavage releases the CPP portion and its attached cargo to enable cell entry. Our data indicate that the transport of these HPMA polymer conjugates by a single ACPP molecule to the cytoplasm occurs via a nonendocytotic and concentration-independent process. The uptake was observed to finish within 20 minutes by inverted fluorescence microscopy. In contrast, HPMA polymer-coated Ad5 without ACPPs was internalized solely by endocytosis. The optimal formulation was not affected by the presence of Ad5 neutralizing antibodies during transduction, and ACPP/polymer-coated Ad5 also retained high targeting capability to several MMP-overexpressing tumor cell types. For the first time, ACPP-mediated cytoplasmic delivery of polymer-bound Ad5 to MMP-overexpressing tumor cells was demonstrated. These findings are significant, as they demonstrate the use of a polymer-based system for the targeted delivery into MMP-overexpressing solid tumors and highlight how to overcome major cellular obstacles to achieve intracellular macromolecular delivery.

  5. Heparin interferes with the radioenzymatic and homogeneous enzyme immunoassays for aminoglycosides

    International Nuclear Information System (INIS)

    Krogstad, D.J.; Granich, G.G.; Murray, P.R.; Pfaller, M.A.; Valdes, R.

    1981-01-01

    Heparin interferes with measurement of aminoglycosides in serum by biological, radioenzymatic, and homogeneous enzyme immunoassay techniques, but not with radioimmunoassay. At concentrations greater than or equal to 10 5 and greater than or equal to 3 X 10 6 USP units/L, respectively, it interferes with the radioenzymatic assay by inhibiting the gentamicin 3-acetyltransferase and kanamycin 6'-acetyltransferase enzymes used in the assay. It interferes with the homogeneous enzyme immunoassays for gentamicin and tobramycin (at concentrations greater than or equal to 10 5 and greater than or equal to10 4 USP units/L, respectively), but not with the commercially available homogeneous enzyme immunoassays for other drugs. Heparin interference with the homogeneous enzyme immunoassay for aminoglycosides requires both the heparin polyanion and glucose-6-phosphate dehydrogenase bound to a cationic aminoglycoside. This interference can be reproduced with dextran sulfate (but not dextran), and does not occur with free enzyme (glucose-6-phosphate dehydrogenase) alone. Heparin interference with these two assays and at concentrations that may be present in intravenous infusions or in seriously underfilled blood-collection tubes is described

  6. Copper sulfates as cathode materials for Li batteries

    Science.gov (United States)

    Schwieger, Jonathan N.; Kraytsberg, Alexander; Ein-Eli, Yair

    As lithium battery technology sets out to bridge the gap between portable electronics and the electrical automotive industry, cathode materials still stand as the bottleneck regarding performances. In the realm of highly attractive polyanion-type structures as high-voltage cathode materials, the sulfate group (SO 4) 2- possesses an acknowledged superiority over other contenders in terms of open circuit voltage arising from the inductive effect of strong covalent S-O bonds. In parallel, novel lithium insertion mechanisms are providing alternatives to traditional intercalation, enabling reversible multi-electron processes securing high capacities. Combining both of these advantageous features, we report here the successful electrochemical reactivity of copper sulfate pentahydrate (CuSO 4·5H 2O) with respect to lithium insertion via a two-electron displacement reaction entailing the extrusion of metallic copper at a dual voltage of 3.2 V and 2.7 V followed by its reversible insertion at 3.5 V and 3.8 V. At this stage, cyclability was still shown to be limited due to the irreversible degradation to a monohydrate structure owing to constitutional water loss.

  7. Graphene-based LbL deposited films: further study of electrical and gas sensing properties

    Directory of Open Access Journals (Sweden)

    Nabok A.

    2017-01-01

    Full Text Available Graphene-surfactant composite materials obtained by the ultrasonic exfoliation of graphite powder in the presence of ionic surfactants (either CTAB or SDS were utilised to construct thin films using layer-by-layer (LbL electrostatic deposition technique. A series of graphene-based thin films were made by alternating layers of either graphene-SDS with polycations (PEI or PAH or graphene-CTAB with polyanions (PSS. Also, graphene-phthalocyanine composite films were produced by alternating layers of graphene-CTAB with tetrasulfonated nickel phthalocyanine. Graphene-surfactant LbL films exhibited good electric conductivity (about 0.1 S/cm of semiconductor type with a band gap of about 20 meV. Judging from UV-vis spectra measurements, graphene-phthalocyanine LbL films appeared to form joint π-electron system. Gas sensing testing of such composite films combining high conductivity of graphene with the gas sensing abilities of phthalocyanines showed substantial changes (up to 10% in electrical conductivity upon exposure to electro-active gases such as HCl and NH3.

  8. Polyoxometalate electrocatalysts based on earth-abundant metals for efficient water oxidation in acidic media

    Science.gov (United States)

    Blasco-Ahicart, Marta; Soriano-López, Joaquín; Carbó, Jorge J.; Poblet, Josep M.; Galan-Mascaros, J. R.

    2018-01-01

    Water splitting is a promising approach to the efficient and cost-effective production of renewable fuels, but water oxidation remains a bottleneck in its technological development because it largely relies on noble-metal catalysts. Although inexpensive transition-metal oxides are competitive water oxidation catalysts in alkaline media, they cannot compete with noble metals in acidic media, in which hydrogen production is easier and faster. Here, we report a water oxidation catalyst based on earth-abundant metals that performs well in acidic conditions. Specifically, we report the enhanced catalytic activity of insoluble salts of polyoxometalates with caesium or barium counter-cations for oxygen evolution. In particular, the barium salt of a cobalt-phosphotungstate polyanion outperforms the state-of-the-art IrO2 catalyst even at pH < 1, with an overpotential of 189 mV at 1 mA cm-2. In addition, we find that a carbon-paste conducting support with a hydrocarbon binder can improve the stability of metal-oxide catalysts in acidic media by providing a hydrophobic environment.

  9. Selective extraction of actinides from high level liquid wastes. Study of the possibilities offered by the Redox properties of actinides

    International Nuclear Information System (INIS)

    Adnet, J.M.

    1991-07-01

    Partitioning of high level liquid wastes coming from nuclear fuel reprocessing by the PUREX process, consists in the elimination of minor actinides (Np, Am, and traces of Pu and U). Among the possible processes, the selective extraction of actinides with oxidation states higher than three is studied. First part of this work deals with a preliminary step; the elimination of the ruthenium from fission products solutions using the electrovolatilization of the RuO4 compound. The second part of this work concerns the complexation and oxidation reactions of the elements U, Np, Pu and Am in presence of a compound belonging to the insaturated polyanions family: the potassium phosphotungstate. For actinide ions with oxidation state (IV) complexed with phosphotungstate anion the extraction mechanism by dioctylamine was studied and the use of a chromatographic extraction technic permitted successful separations between tetravalents actinides and trivalents actinides. Finally, in accordance with the obtained results, the basis of a separation scheme for the management of fission products solutions is proposed

  10. Formation and dielectric properties of polyelectrolyte multilayers studied by a silicon-on-insulator based thin film resistor.

    Science.gov (United States)

    Neff, Petra A; Wunderlich, Bernhard K; Klitzing, Regine V; Bausch, Andreas R

    2007-03-27

    The formation of polyelectrolyte multilayers (PEMs) is investigated using a silicon-on-insulator based thin film resistor which is sensitive to variations of the surface potential. The buildup of the PEMs at the silicon oxide surface of the device can be observed in real time as defined potential shifts. The influence of polymer charge density is studied using the strong polyanion poly(styrene sulfonate), PSS, combined with the statistical copolymer poly(diallyl-dimethyl-ammoniumchloride-stat-N-methyl-N-vinylacetamide), P(DADMAC-stat-NMVA), at various degrees of charge (DC). The multilayer formation stops after a few deposition steps for a DC below 75%. We show that the threshold of surface charge compensation corresponds to the threshold of multilayer formation. However, no reversion of the preceding surface charge was observed. Screening of polyelectrolyte charges by mobile ions within the polymer film leads to a decrease of the potential shifts with the number of layers deposited. This decrease is much slower for PEMs consisting of P(DADMAC-stat-NMVA) and PSS as compared to PEMs consisting of poly(allylamine-hydrochloride), PAH, and PSS. From this, significant differences in the dielectric constants of the polyelectrolyte films and in the concentration of mobile ions within the films can be derived.

  11. Heat capacity changes in RNA folding: application of perturbation theory to hammerhead ribozyme cold denaturation.

    Science.gov (United States)

    Mikulecky, Peter J; Feig, Andrew L

    2004-01-01

    In proteins, empirical correlations have shown that changes in heat capacity (DeltaC(P)) scale linearly with the hydrophobic surface area buried upon folding. The influence of DeltaC(P) on RNA folding has been widely overlooked and is poorly understood. In addition to considerations of solvent reorganization, electrostatic effects might contribute to DeltaC(P)s of folding in polyanionic species such as RNAs. Here, we employ a perturbation method based on electrostatic theory to probe the hot and cold denaturation behavior of the hammerhead ribozyme. This treatment avoids much of the error associated with imposing two-state folding models on non-two-state systems. Ribozyme stability is perturbed across a matrix of solvent conditions by varying the concentration of NaCl and methanol co-solvent. Temperature-dependent unfolding is then monitored by circular dichroism spectroscopy. The resulting array of unfolding transitions can be used to calculate a DeltaC(P) of folding that accurately predicts the observed cold denaturation temperature. We confirm the accuracy of the calculated DeltaC(P) by using isothermal titration calorimetry, and also demonstrate a methanol-dependence of the DeltaC(P). We weigh the strengths and limitations of this method for determining DeltaC(P) values. Finally, we discuss the data in light of the physical origins of the DeltaC(P)s for RNA folding and consider their impact on biological function.

  12. Flexible single-layer ionic organic-inorganic frameworks towards precise nano-size separation

    Science.gov (United States)

    Yue, Liang; Wang, Shan; Zhou, Ding; Zhang, Hao; Li, Bao; Wu, Lixin

    2016-02-01

    Consecutive two-dimensional frameworks comprised of molecular or cluster building blocks in large area represent ideal candidates for membranes sieving molecules and nano-objects, but challenges still remain in methodology and practical preparation. Here we exploit a new strategy to build soft single-layer ionic organic-inorganic frameworks via electrostatic interaction without preferential binding direction in water. Upon consideration of steric effect and additional interaction, polyanionic clusters as connection nodes and cationic pseudorotaxanes acting as bridging monomers connect with each other to form a single-layer ionic self-assembled framework with 1.4 nm layer thickness. Such soft supramolecular polymer frameworks possess uniform and adjustable ortho-tetragonal nanoporous structure in pore size of 3.4-4.1 nm and exhibit greatly convenient solution processability. The stable membranes maintaining uniform porous structure demonstrate precisely size-selective separation of semiconductor quantum dots within 0.1 nm of accuracy and may hold promise for practical applications in selective transport, molecular separation and dialysis systems.

  13. Chitosan Based Self-Assembled Nanoparticles in Drug Delivery

    Directory of Open Access Journals (Sweden)

    Javier Pérez Quiñones

    2018-02-01

    Full Text Available Chitosan is a cationic polysaccharide that is usually obtained by alkaline deacetylation of chitin poly(N-acetylglucosamine. It is biocompatible, biodegradable, mucoadhesive, and non-toxic. These excellent biological properties make chitosan a good candidate for a platform in developing drug delivery systems having improved biodistribution, increased specificity and sensitivity, and reduced pharmacological toxicity. In particular, chitosan nanoparticles are found to be appropriate for non-invasive routes of drug administration: oral, nasal, pulmonary and ocular routes. These applications are facilitated by the absorption-enhancing effect of chitosan. Many procedures for obtaining chitosan nanoparticles have been proposed. Particularly, the introduction of hydrophobic moieties into chitosan molecules by grafting to generate a hydrophobic-hydrophilic balance promoting self-assembly is a current and appealing approach. The grafting agent can be a hydrophobic moiety forming micelles that can entrap lipophilic drugs or it can be the drug itself. Another suitable way to generate self-assembled chitosan nanoparticles is through the formation of polyelectrolyte complexes with polyanions. This paper reviews the main approaches for preparing chitosan nanoparticles by self-assembly through both procedures, and illustrates the state of the art of their application in drug delivery.

  14. Synergistic activity profile of carbosilane dendrimer G2-STE16 in combination with other dendrimers and antiretrovirals as topical anti-HIV-1 microbicide.

    Science.gov (United States)

    Sepúlveda-Crespo, Daniel; Lorente, Raquel; Leal, Manuel; Gómez, Rafael; De la Mata, Francisco J; Jiménez, José Luis; Muñoz-Fernández, M Ángeles

    2014-04-01

    Polyanionic carbosilane dendrimers represent opportunities to develop new anti-HIV microbicides. Dendrimers and antiretrovirals (ARVs) acting at different stages of HIV replication have been proposed as compounds to decrease new HIV infections. Thus, we determined the potential use of our G2-STE16 carbosilane dendrimer in combination with other carbosilane dendrimers and ARVs for the use as topical microbicide against HIV-1. We showed that these combinations obtained 100% inhibition and displayed a synergistic profile against different HIV-1 isolates in our model of TZM.bl cells. Our results also showed their potent activity in the presence of an acidic vaginal or seminal fluid environment and did not activate an inflammatory response. This study is the first step toward exploring the use of different anionic carbosilane dendrimers in combination and toward making a safe microbicide. Therefore, our results support further studies on dendrimer/dendrimer or dendrimer/ARV combinations as topical anti-HIV-1 microbicide. This paper describes the first steps toward the use of anionic carbosilane dendrimers in combination with antivirals to address HIV-1, paving the way to further studies on dendrimer/dendrimer or dendrimer/ARV combinations as topical anti-HIV-1 microbicides. © 2014.

  15. I. Hole-transporting dendrimers and their use in organic light-emitting devices (OLEDs) and II. Novel layered catalysts containing bipyridinium and zero-valent metal species

    Science.gov (United States)

    Koene, Shannon Carol

    A series of polyaromatic ether/ester dendrimers containing a hole transporting naphthylphenylbenzyl amine at the periphery and a variety of fluorescent dyes at the core has been studied in an effort to observe energy transfer in these species. The dyes incorporated in these dendrimers include 1,4-dihydroxyanthraquinone (quinizarin), Coumarin 343, and a benzopentathiophene. These dendrimers have been incorporated into both single layer and heterostructure organic light emitting devices (OLEDs). In the case of first generation dendrimer OLEDs, excimer/exciplex formation was predominant. In third generation dendrimers, complete energy transfer from the periphery to the dye at the core was observed both in photoluminescence spectra and electroluminescence in OLEDs. Dendrimers containing different dye cores can be combined to achieve color mixing/tuning. In addition, layered catalysts were prepared via both covalent and electrostatic means to achieve the catalytic production of hydrogen peroxide from hydrogen and oxygen. Covalent catalysts were prepared by first growing layers of zirconium and a bipyridinium containing bisphosphonate onto silica particles. Palladium and/or platinum was ion-exchanged into the structure and reduced to the zero valent metal by hydrogen gas. A second set of catalysts was prepared by electrostatically depositing polycations/polyanions onto carboxylate or amine functionalized polystyrene microspheres. Anionic colloidal particles were adsorbed to the polycationic surface. An octacationic viologen oligomer was used in an attempt to increase the affinity of adsorption of the Pd particles to the surface of the microspheres. Catalytic studies of both types of catalysts are herein reported.

  16. Electrochemistry of sulfur and polysulfides in ionic liquids.

    Science.gov (United States)

    Manan, Ninie S A; Aldous, Leigh; Alias, Yatimah; Murray, Paul; Yellowlees, Lesley J; Lagunas, M Cristina; Hardacre, Christopher

    2011-12-01

    The electrochemistry of elemental sulfur (S(8)) and the polysulfides Na(2)S(4) and Na(2)S(6) has been studied for the first time in nonchloroaluminate ionic liquids. The cyclic voltammetry of S(8) in the ionic liquids is different to the behavior reported in some organic solvents, with two reductions and one oxidation peak observed. Supported by in situ UV-vis spectro-electrochemical experiments, the main reduction products of S(8) in [C(4)mim][DCA] ([C(4)mim] = 1-butyl-3-methylimidazolium; DCA = dicyanamide) have been identified as S(6)(2-) and S(4)(2-), and plausible pathways for the formation of these species are proposed. Dissociation and/or disproportionation of the polyanions S(6)(2-) and S(4)(2-) appears to be slow in the ionic liquid, with only small amounts of the blue radical species S(3)(•-) formed in the solutions at r.t., in contrast with that observed in most molecular solvents. © 2011 American Chemical Society

  17. Molecular interactions in self-assembled nano-structures of chitosan-sodium alginate based polyelectrolyte complexes.

    Science.gov (United States)

    Wasupalli, Geeta Kumari; Verma, Devendra

    2018-03-16

    We report here the self-assembled structures of polyelectrolyte complexes (PECs) of polyanionic sodium alginate with the polycationic chitosan at room temperature. The PECs prepared at different pH values exhibited two distinct morphologies. The chitosan-alginate PECs self-assembled into the fibrous structure in a low pH range of pH3 to 7. The PECs obtained at high pH series around pH8 and above resulted in the formation of colloidal nanoparticles in the range of 120±9.48nm to 46.02±16.66nm. The zeta potential measurement showed that PECs prepared at lower pH (pHPECs prepared at higher pH than 6 exhibited highly negative surface charge. The molecular interactions in nano-colloids and fibers were evaluated using FTIR analysis. The results attest that the ionic state of the chitosan and alginate plays an important role controlling the morphologies of the PECS. The present study has identified the enormous potential of the polyelectrolytes complexes to exploit shape by the alteration of ionic strength. These findings might be useful in the development of novel biomaterial. The produced fibers and nanocolloids could be applied as a biomaterial for tissue engineering and drug delivery. Copyright © 2017. Published by Elsevier B.V.

  18. Elaboration of Stable and Antibody Functionalized Positively Charged Colloids by Polyelectrolyte Complexation between Chitosan and Hyaluronic Acid

    Directory of Open Access Journals (Sweden)

    Ramona C. Polexe

    2013-07-01

    Full Text Available In this study, we describe the elaboration of multifunctional positively charged polyelectrolyte complex (PEC nanoparticles, designed to be stable at physiological salt concentration and pH, for effective targeted delivery. These nanoparticles were obtained by charge neutralization between chitosan (CS as polycation and hyaluronic acid (HA as polyanion. We showed that the course of the complexation process and the physico-chemical properties of the resulting colloids were impacted by (i internal parameters such as the Degree of Acetylation (DA, i.e., the molar ration of acetyl glucosamine residues and molar mass of CS, the HA molar mass and (ii external parameters like the charge mixing ratio and the polymer concentrations. As a result, nonstoichiometric colloidal PECs were obtained in water or PBS (pH 7.4 and remained stable over one month. The polymer interactions were characterized by thermal analysis (DSC and TGA and the morphology was studied by scanning electron microscopy. A model antibody, anti-ovalbumine (OVA immunoglobulin A (IgA was sorbed on the particle surface in water and PBS quantitatively in 4 h. The CS-HA/IgA nanoparticles average size was between 425–665 nm with a positive zeta potential. These results pointed out that CS-HA can be effective carriers for use in targeted drug delivery.

  19. Small interfering RNA delivery through positively charged polymer nanoparticles

    International Nuclear Information System (INIS)

    Dragoni, Luca; Cesana, Alberto; Moscatelli, Davide; Ferrari, Raffaele; Morbidelli, Massimo; Lupi, Monica; Falcetta, Francesca; Ubezio, Paolo; D’Incalci, Maurizio

    2016-01-01

    Small interfering RNA (siRNA) is receiving increasing attention with regard to the treatment of many genetic diseases, both acquired and hereditary, such as cancer and diabetes. Being a high molecular weight (MW) polyanion, siRNA is not able to cross a cell membrane, and in addition it is unstable in physiological conditions. Accordingly, a biocompatible nanocarrier able to deliver siRNA into cells is needed. In this work, we synthesized biocompatible positively charged nanoparticles (NPs) following a two-step process that involves ring opening polymerization (ROP) and emulsion free radical polymerization (EFRP). Firstly, we proved the possibility of fine tuning the NPs’ characteristics (e.g. size and surface charge) by changing the synthetic process parameters. Then the capability in loading and delivering undamaged siRNA into a cancer cell cytoplasm has been shown. This latter process occurs through the biodegradation of the polymer constituting the NPs, whose kinetics can be tuned by adjusting the polymer’s MW. Finally, the ability of NPs to carry siRNA inside the cells in order to inhibit their target gene has been demonstrated using green flourescent protein positive cells. (paper)

  20. Fullerenol/doxorubicin nanocomposite mitigates acute oxidative stress and modulates apoptosis in myocardial tissue

    Science.gov (United States)

    Seke, Mariana; Petrovic, Danijela; Djordjevic, Aleksandar; Jovic, Danica; Labudovic Borovic, Milica; Kanacki, Zdenko; Jankovic, Milan

    2016-12-01

    Fullerenol (C60(OH)24) is present in aqueous solutions in the form of polyanion nanoparticles with particles’ size distribution within the range from 15 to 42 nm. In this research it is assumed that these features could enable fullerenol nanoparticles (FNPs) to bind positively charged molecules like doxorubicin (DOX) and serve as drug carriers. Considering this, fullerenol/doxorubicin nanocomposite (FNP/DOX) is formed and characterized by ultra-performance liquid chromatography tandem mass spectrometry, dynamic light scattering, atomic force microscopy and transmission electron microscopy. Measurements have shown that DOX did not significantly affect particle size (23 nm). It is also assumed that FNP/DOX could reduce the acute cardiotoxic effects of DOX in vivo (Wistar rats treated i.p.). In this study, quantitative real time polymerase chain reaction results have shown that treatment with DOX alone caused significant increase in mRNA levels of catalase (p effect is significantly reduced by the treatment with FNP/DOX (p < 0.05). Furthermore, mRNA levels of antiapoptotic enzyme (Bcl-2) are significantly increased (p < 0.05) in all treated groups, particularly where FNP/DOX was applied, suggesting cell resistance to apoptosis. Moreover, ultrastructural analysis has shown the absence of myelin figures within the mitochondria in the heart tissue with FNP/DOX treatment, indicating reduction of oxidative stress. Hence, our results have implied that FNP/DOX is generally less harmful to the heart compared to DOX.

  1. Lithium Iron Orthosilicate Cathode: Progress and Perspectives

    Energy Technology Data Exchange (ETDEWEB)

    Ni, Jiangfeng [College; amp, Physics (CECMP), Soochow University, Suzhou 215006, PR China; Jiang, Yu [College; amp, Physics (CECMP), Soochow University, Suzhou 215006, PR China; Bi, Xuanxuan [Chemical; Li, Liang [College; amp, Physics (CECMP), Soochow University, Suzhou 215006, PR China; Lu, Jun [Chemical

    2017-07-18

    The pursuit of cathodes with a high capacity is remarkably driven by the ever increasing demand of high-energy lithium ion batteries in electronics and transportation. In this regard, polyanionic lithium iron orthosilicate (Li2FeSiO4) offers a promising opportunity because it affords a high theoretical capacity of 331 mAh g–1. However, such a high theoretical capacity of Li2FeSiO4 has frequently been compromised in practice because of the extremely low electronic and ionic conductivity. To address this issue, material engineering strategies to boost the Li storage kinetics in Li2FeSiO4 have proven indispensable. In this Perspective, we will briefly present the structural characteristics, intrinsic physicochemical properties, and electrochemical behavior of Li2FeSiO4. We particularly focus on recent materials engineering of silicates, which is implemented mainly through advanced synthetic techniques and elaborate controls. This Perspective highlights the importance of integrating theoretical analysis into experimental implementation to further advance the Li2FeSiO4 materials.

  2. Polyoxometalate coordination induced controllable release of quinolone in hybrid film

    Science.gov (United States)

    Yang, Fan; Li, Yang; Lv, Yu-Guang; Zhou, Shu-Jing; Li, Si; Gao, Guang-Gang; Liu, Hong

    2018-05-01

    Due to some side effects of quinolones in vivo, it is an urgent issue to extend their new applications in vitro. In this paper, structure-determined vanadium-quinolone functionalized polymolybdates of (NH4)2 [(γ-Mo8O26){VO(CF)2}2] (1) and (NH4)2 [(γ-Mo8O26){VO(NF)2}2] (2) (CF = ciprofloxacin; NF = norfloxacin) have been designed and synthesized. Complex 1 or 2 features a γ-type [Mo8O26]4- polyanion functionalized by two monocapped vanadium-quinolone complexes. Different H-bonds and π···π interactions allow 1 or 2 to form a 2D layered structure at solid state. When complex 1 or 2 is transferred into polyvinyl alcohol (PVA) film, its release rate in solution is lower than that of CF- or NF-PVA film and thus forming a novel quinolone delivery system. This is the first time that slow release effect of quinolone is achieved by polyoxometalate coordination effect. The slow release of 1 or 2 in PVA film is mainly ascribed to the coordination of quinolone with polyoxometalate anions.

  3. Ferromagnetic ordering in ThSi{sub 2} type CeAu{sub 0.28}Ge{sub 1.72}

    Energy Technology Data Exchange (ETDEWEB)

    Sebastian, C. Peter, E-mail: s-peter@northwestern.ed [Department of Chemistry, Northwestern University, 2145 N. Sheridan Road, Evanston, IL 60208-3113 (United States); Kanatzidis, Mercouri G., E-mail: m-kanatzidis@northwestern.ed [Department of Chemistry, Northwestern University, 2145 N. Sheridan Road, Evanston, IL 60208-3113 (United States)

    2010-04-15

    The compound CeAu{sub 0.28}Ge{sub 1.72} crystallizes in the ThSi{sub 2} structure type in the tetragonal space group I4{sub 1}/amd with lattice parameters a=b=4.2415(6) A c=14.640(3) A. CeAu{sub 0.28}Ge{sub 1.72} is a polar intermetallic compound having a three-dimensional Ge/Au polyanion sub-network filled with Ce atoms. The magnetic susceptibility data show Curie-Weiss law behavior above 50 K. The compound orders ferromagnetically at {approx}8 K with estimated magnetic moment of 2.48 mu{sub B}/Ce. The ferromagnetic ordering is confirmed by the heat capacity data which show a rise at {approx}8 K. The electronic specific heat coefficient (gamma) value obtained from the paramagnetic temperature range 15-25 K is {approx}124(5) mJ/ mol K{sup 2}. The entropy change due to the ferromagnetic transition is {approx}4.2 J/mol K which is appreciably reduced compared to the value of R ln(2) expected for a crystal-field-split doublet ground state and/or Kondo exchange interactions. - Graphical abstract: CeAu{sub 0.28}Ge{sub 1.72} crystallizes in the ThSi{sub 2} structure type in the tetragonal space group I4{sub 1}/amd and orders ferromagnetically at {approx}8 K.

  4. Chitosan nanoparticle-based neuronal membrane sealing and neuroprotection following acrolein-induced cell injury

    Directory of Open Access Journals (Sweden)

    Shi Riyi

    2010-01-01

    Full Text Available Abstract Background The highly reactive aldehyde acrolein is a very potent endogenous toxin with a long half-life. Acrolein is produced within cells after insult, and is a central player in slow and progressive "secondary injury" cascades. Indeed, acrolein-biomolecule complexes formed by cross-linking with proteins and DNA are associated with a number of pathologies, especially central nervous system (CNS trauma and neurodegenerative diseases. Hydralazine is capable of inhibiting or reducing acrolein-induced damage. However, since hydralazine's principle activity is to reduce blood pressure as a common anti-hypertension drug, the possible problems encountered when applied to hypotensive trauma victims have led us to explore alternative approaches. This study aims to evaluate such an alternative - a chitosan nanoparticle-based therapeutic system. Results Hydralazine-loaded chitosan nanoparticles were prepared using different types of polyanions and characterized for particle size, morphology, zeta potential value, and the efficiency of hydralazine entrapment and release. Hydralazine-loaded chitosan nanoparticles ranged in size from 300 nm to 350 nm in diameter, and with a tunable, or adjustable, surface charge. Conclusions We evaluated the utility of chitosan nanoparticles with an in-vitro model of acrolein-mediated cell injury using PC -12 cells. The particles effectively, and statistically, reduced damage to membrane integrity, secondary oxidative stress, and lipid peroxidation. This study suggests that a chitosan nanoparticle-based therapy to interfere with "secondary" injury may be possible.

  5. Surface modification of protein enhances encapsulation in chitosan nanoparticles

    Science.gov (United States)

    Koyani, Rina D.; Andrade, Mariana; Quester, Katrin; Gaytán, Paul; Huerta-Saquero, Alejandro; Vazquez-Duhalt, Rafael

    2018-04-01

    Chitosan nanoparticles have a huge potential as nanocarriers for environmental and biomedical purposes. Protein encapsulation in nano-sized chitosan provides protection against inactivation, proteolysis, and other alterations due to environmental conditions, as well as the possibility to be targeted to specific tissues by ligand functionalization. In this work, we demonstrate that the chemical modification of the protein surface enhances the protein loading in chitosan nanocarriers. Encapsulation of green fluorescent protein and the cytochrome P450 was studied. The increase of electrostatic interactions between the free amino groups of chitosan and the increased number of free carboxylic groups in the protein surface enhance the protein loading, protein retention, and, thus, the enzymatic activity of chitosan nanoparticles. The chemical modification of protein surface with malonic acid moieties reduced drastically the protein isoelectric point increasing the protein interaction with the polycationic biomaterial and chitosan. The chemical modification of protein does not alter the morphology of chitosan nanoparticles that showed an average diameter of 18 nm, spheroidal in shape, and smooth surfaced. The strategy of chemical modification of protein surface, shown here, is a simple and efficient technique to enhance the protein loading in chitosan nanoparticles. This technique could be used for other nanoparticles based on polycationic or polyanionic materials. The increase of protein loading improves, doubtless, the performance of protein-loaded chitosan nanoparticles for biotechnological and biomedical applications.

  6. Insight on the formation of chitosan nanoparticles through ionotropic gelation with tripolyphosphate.

    Science.gov (United States)

    Koukaras, Emmanuel N; Papadimitriou, Sofia A; Bikiaris, Dimitrios N; Froudakis, George E

    2012-10-01

    This work reports details pertaining to the formation of chitosan nanoparticles that we prepare by the ionic gelation method. The molecular interactions of the ionic cross-linking of chitosan with tripolyphosphate have been investigated and elucidated by means of all-electron density functional theory. Solvent effects have been taken into account using implicit models. We have identified primary-interaction ionic cross-linking configurations that we define as H-link, T-link, and M-link, and we have quantified the corresponding interaction energies. H-links, which display high interaction energies and are also spatially broadly accessible, are the most probable cross-linking configurations. At close range, proton transfer has been identified, with maximum interaction energies ranging from 12.3 up to 68.3 kcal/mol depending on the protonation of the tripolyphosphate polyanion and the relative coordination of chitosan with tripolyphosphate. On the basis of our results for the linking types (interaction energies and torsion bias), we propose a simple mechanism for their impact on the chitosan/TPP nanoparticle formation process. We introduce the β ratio, which is derived from the commonly used α ratio but is more fundamental since it additionally takes into account structural details of the oligomers.

  7. The scavenger receptor MARCO modulates TLR-induced responses in dendritic cells.

    Directory of Open Access Journals (Sweden)

    Haydn T Kissick

    Full Text Available The scavenger receptor MARCO mediates macrophage recognition and clearance of pathogens and their polyanionic ligands. However, recent studies demonstrate MARCO expression and function in dendritic cells, suggesting MARCO might serve to bridge innate and adaptive immunity. To gain additional insight into the role of MARCO in dendritic cell activation and function, we profiled transcriptomes of mouse splenic dendritic cells obtained from MARCO deficient mice and their wild type counterparts under resting and activating conditions. In silico analysis uncovered major alterations in gene expression in MARCO deficient dendritic cells resulting in dramatic alterations in key dendritic cell-specific pathways and functions. Specifically, changes in CD209, FCGR4 and Complement factors can have major consequences on DC-mediated innate responses. Notably, these perturbations were magnified following activation with the TLR-4 agonist lipopolysaccharide. To validate our in silico data, we challenged DC's with various agonists that recognize all mouse TLRs and assessed expression of a set of immune and inflammatory marker genes. This approach identified a differential contribution of MARCO to TLR activation and validated a major role for MARCO in mounting an inflammatory response. Together, our data demonstrate that MARCO differentially affects TLR-induced DC activation and suggest targeting of MARCO could lead to different outcomes that depend on the inflammatory context encountered by DC.

  8. Medium Effects on Minimum Inhibitory Concentrations of Nylon-3 Polymers against E. coli

    Science.gov (United States)

    Choi, Heejun; Chakraborty, Saswata; Liu, Runhui; Gellman, Samuel H.; Weisshaar, James C.

    2014-01-01

    Minimum inhibitory concentrations (MICs) against E. coli were measured for three nylon-3 polymers using Luria-Bertani broth (LB), brain-heart infusion broth (BHI), and a chemically defined complete medium (EZRDM). The polymers differ in the ratio of hydrophobic to cationic subunits. The cationic homopolymer is inert against E. coli in BHI and LB, but becomes highly potent in EZRDM. A mixed hydrophobic/cationic polymer with a hydrophobic t-butylbenzoyl group at its N-terminus is effective in BHI, but becomes more effective in EZRDM. Supplementation of EZRDM with the tryptic digest of casein (often found in LB) recapitulates the LB and BHI behavior. Additional evidence suggests that polyanionic peptides present in LB and BHI may form electrostatic complexes with cationic polymers, decreasing activity by diminishing binding to the anionic lipopolysaccharide layer of E. coli. In contrast, two natural antimicrobial peptides show no medium effects. Thus, the use of a chemically defined medium helps to reveal factors that influence antimicrobial potency of cationic polymers and functional differences between these polymers and evolved antimicrobial peptides. PMID:25153714

  9. Superstructure formation in PrNi_2Al_3 and ErPd_2Al_3

    International Nuclear Information System (INIS)

    Eustermann, Fabian; Hoffmann, Rolf-Dieter; Janka, Oliver; Oldenburg Univ.

    2017-01-01

    The intermetallic phase ErPd_2Al_3 was obtained by arc-melting of the elements and subsequent annealing for crystal growth. The sample was studied by X-ray diffraction on powders and single crystals. The structure of ErPd_2Al_3 was refined from X-ray diffraction data and revealed a superstructure of PrNi_2Al_3 - a CaCu_5 derivative (P6/m, a=1414.3(1), c=418.87(3) pm wR=0.0820, 1060 F"2 values, 48 variables). The same superstructure was subsequently found for PrNi_2Al_3 (P6/m, a=1407.87(4), c=406.19(2) pm, wR=0.0499, 904 F"2 values, 47 variables). In the crystal structure, the aluminium and transition metal atoms form a polyanionic network according to [T_2Al_3]"δ"-, while rare earth atoms fill cavities within the networks. They are coordinated by six transition metal and twelve aluminum atoms. In contrast to the PrNi_2Al_3 type structure reported so far, two crystallographic independent rare-earth sites are found of which one (1b) is shifted by 1/2 z, causing a distortion in the structure along with a recoloring of the T and Al atoms in the network.

  10. The genome of the seagrass Zostera marina reveals angiosperm adaptation to the sea

    KAUST Repository

    Olsen, Jeanine L.

    2016-01-27

    Seagrasses colonized the sea1 on at least three independent occasions to form the basis of one of the most productive and widespread coastal ecosystems on the planet2. Here we report the genome of Zostera marina (L.), the first, to our knowledge, marine angiosperm to be fully sequenced. This reveals unique insights into the genomic losses and gains involved in achieving the structural and physiological adaptations required for its marine lifestyle, arguably the most severe habitat shift ever accomplished by flowering plants. Key angiosperm innovations that were lost include the entire repertoire of stomatal genes3, genes involved in the synthesis of terpenoids and ethylene signalling, and genes for ultraviolet protection and phytochromes for far-red sensing. Seagrasses have also regained functions enabling them to adjust to full salinity. Their cell walls contain all of the polysaccharides typical of land plants, but also contain polyanionic, low-methylated pectins and sulfated galactans, a feature shared with the cell walls of all macroalgae4 and that is important for ion homoeostasis, nutrient uptake and O2/CO2 exchange through leaf epidermal cells. The Z. marina genome resource will markedly advance a wide range of functional ecological studies from adaptation of marine ecosystems under climate warming5, 6, to unravelling the mechanisms of osmoregulation under high salinities that may further inform our understanding of the evolution of salt tolerance in crop plants7.

  11. Thin film free-standing PEDOT:PSS/SU8 bilayer microactuators

    International Nuclear Information System (INIS)

    Taccola, S; Greco, F; Mazzolai, B; Mattoli, V; Jager, E W H

    2013-01-01

    Several smart active materials have been proposed and tested for the development of microactuators. Among these, conjugated polymers are of great interest because miniaturization improves their electrochemical properties, such as increasing the speed and stress output of microactuators, with respect to large-scale actuators. Recently we developed a novel fabrication process to obtain robust free-standing conductive ultra-thin films made of the conjugated polymer poly(3, 4-ethylenedioxythiophene) doped with the polyanion poly(styrenesulfonate) (PEDOT:PSS). These conductive free-standing nanofilms, with thicknesses ranging between a few tens to several hundreds of nm, allow the realisation of new all polymer microactuators using facile microfabrication methods. Here, we report a novel processing method for manufacturing all polymer electrochemical microactuators. We fabricated and patterned free-standing PEDOT:PSS/SU8 bilayer microactuators in the form of microfingers of a variety of lengths using adapted microfabrication procedures. By imposing electrochemical oxidation/reduction cycles on the PEDOT:PSS we were able to demonstrate reversible actuation of the microactuators resulting in bending of the microfingers. A number of possible applications can be envisaged for these small, soft actuators, such as microrobotics and cell manipulation. (technical note)

  12. Thioaluminogermanate M(AlS2)(GeS2)4 (M = Na, Ag, Cu): Synthesis, Crystal Structures, Characterization, Ion-Exchange and Solid-State 27Al and 23Na NMR Spectroscopy

    KAUST Repository

    Alahmary, Fatimah S.

    2018-03-14

    The new thioaluminogermanate Na(AlS2)(GeS2)4 (1) was successfully synthesized by a direct combination reaction. The compound crystallizes in the monoclinic space group P21/n (no. 14) with unit cell parameters a = 6.803(3) Å, b = 38.207(2) Å, c = 6.947(4) Å, and β = 119.17(3)°. The crystal structure is composed of a [(AlS2)(GeS2)4]− 3D polyanionic network, in which Al and Ge atoms share the atomic positions and Na cations occupy the channels and voids formed by the connection of (Ge/Al)S4 tetrahedra. The title compound shows a cation-exchange property with monovalent Ag+ and Cu+ ions at room temperature in solvent media, resulting in the formation of the isostructural compounds Ag(AlS2)(GeS2)4 (2) and Cu(AlS2)(GeS2)4 (3), respectively. The ion-exchange products Ag(AlS2)(GeS2)4 (2) and Cu(AlS2)(GeS2)4 (3) show higher air stability and narrower bandgap energies compared to those of the parent compound Na(AlS2)(GeS2)4 (1).

  13. Bioactive Compound Synthetic Capacity and Ecological Significance of Marine Bacterial Genus Pseudoalteromonas

    Directory of Open Access Journals (Sweden)

    John P. Bowman

    2007-12-01

    Full Text Available The genus Pseudoalteromonas is a marine group of bacteria belonging to theclass Gammaproteobacteria that has come to attention in the natural product andmicrobial ecology science fields in the last decade. Pigmented species of the genus havebeen shown to produce an array of low and high molecular weight compounds withantimicrobial, anti-fouling, algicidal and various pharmaceutically-relevant activities.Compounds formed include toxic proteins, polyanionic exopolymers, substitutedphenolic and pyrolle-containing alkaloids, cyclic peptides and a range of bromine-substituted compounds. Ecologically, Pseudoalteromonas appears significant and to datehas been shown to influence biofilm formation in various marine econiches; involved inpredator-like interactions within the microbial loop; influence settlement, germinationand metamorphosis of various invertebrate and algal species; and may also be adopted bymarine flora and fauna as defensive agents. Studies have been so far limited to arelatively small subset of strains compared to the known diversity of the genussuggesting that many more discoveries of novel natural products as well as ecologicalconnections these may have in the marine ecosystem remain to be made.

  14. Preparation and characterization of chondroitin-sulfate-A-coated magnetite nanoparticles for biomedical applications

    Science.gov (United States)

    Tóth, Ildikó Y.; Illés, Erzsébet; Szekeres, Márta; Tombácz, Etelka

    2015-04-01

    Polysaccharides are promising candidates for manufacturing biocompatible core-shell nanoparticles with potential in vivo use. Superparamagnetic magnetite nanoparticles (MNPs) have prospective application in both diagnosis and therapy, and so developing a novel polysaccharide shell on MNP core is of great challenge. MNPs were prepared by co-precipitation, then the surface of purified MNPs was coated with chondroitin-sulfate-A (CSA) to obtain core-shell structured magnetite nanoparticles (CSA@MNP). The effect of the added amount of CSA on the surface charging and the aggregation state of MNPs at various pHs and 10 mM NaCl was measured by electrophoresis and dynamic light scattering. The amphoteric behavior of MNPs was fundamentally modified by adsorption of CSA polyanions. A very low CSA-loading induces the aggregation of MNPs, while four times more stabilizes the dispersions over the whole pH-range studied. The coagulation kinetics experiments measured at pH=6.3±0.3 showed that salt tolerance of CSA@MNPs rises up to ~150 mM NaCl.

  15. Reorganization of the 3D matrix of polyelectrolytes complexes of chitosan/chondroitin sulfate swollen in different conditions of pH and immersion time

    Energy Technology Data Exchange (ETDEWEB)

    Fajardo, Andre R.; Piai, Juliana F.; Rubira, Adley F.; Muniz, Edvani C., E-mail: ecmuniz@uem.b [Universidade Estadual de Maringa (DG/UEM), PR (Brazil). Dept. de Quimica. Grupo de Materiais Polimericos e Compositos

    2009-07-01

    The chitosan (CT), a polysaccharide that has excellent properties for use as biomaterials, shows cationic nature and properties of high charge density in acidic solutions, thus CT can form complex polyelectrolyte (PEC) with polyanionic moieties such as the chondroitin sulfate (CS), a key component of cartilage matrix. We studied the reorganization of chains on 3D matrix of CT/CS PEC at swollen state in different conditions of pH and immersion time. It was verified that this PEC (QT/CS) has the capacity to reorganize its 3D matrix but it depends of the pH of the medium in which it is swelled and the time that remains immersed. The reorganization of the 3D matrix is caused by the reordering of the chains forming the PEC after the release of the CS, that occurs mainly at pH values higher than or close to the pKa of CT (pKa CT) . Such reorganization was detected by X-ray diffraction profiles and allows an increase in crystallinity, thermal stability and pore size of the PEC. This shows that the PEC produced can be processed to suit its use as bio material, applied i.e. as drugs release devices. (author)

  16. Preparation and characterization of chondroitin‐sulfate‐A‐coated magnetite nanoparticles for biomedical applications

    International Nuclear Information System (INIS)

    Tóth, Ildikó Y.; Illés, Erzsébet; Szekeres, Márta; Tombácz, Etelka

    2015-01-01

    Polysaccharides are promising candidates for manufacturing biocompatible core–shell nanoparticles with potential in vivo use. Superparamagnetic magnetite nanoparticles (MNPs) have prospective application in both diagnosis and therapy, and so developing a novel polysaccharide shell on MNP core is of great challenge. MNPs were prepared by co-precipitation, then the surface of purified MNPs was coated with chondroitin-sulfate-A (CSA) to obtain core–shell structured magnetite nanoparticles (CSA@MNP). The effect of the added amount of CSA on the surface charging and the aggregation state of MNPs at various pHs and 10 mM NaCl was measured by electrophoresis and dynamic light scattering. The amphoteric behavior of MNPs was fundamentally modified by adsorption of CSA polyanions. A very low CSA-loading induces the aggregation of MNPs, while four times more stabilizes the dispersions over the whole pH-range studied. The coagulation kinetics experiments measured at pH=6.3±0.3 showed that salt tolerance of CSA@MNPs rises up to ~150 mM NaCl. - Highlights: • Novel CSA-coated core–shell magnetite nanoparticles were prepared successfully. • The aggregation range of MNPs was shifted gradually to the lower pHs by CSA-loading. • CSA stabilizes electrosterically the MNPs over wide pH-range relevant to biosystems. • The salt tolerance of CSA@MNP enables them to use under physiological condition

  17. Phosphatidylcholine nanovesicles coated with chitosan or chondroitin sulfate as novel devices for bacteriocin delivery

    Science.gov (United States)

    da Silva, Indjara Mallmann; Boelter, Juliana Ferreira; da Silveira, Nádya Pesce; Brandelli, Adriano

    2014-07-01

    There is increased interest on the use of natural antimicrobial peptides in biomedicine and food preservation technologies. In this study, the antimicrobial activity of nisin encapsulated into nanovesicles containing polyanionic polysaccharides was investigated. Nisin was encapsulated in phosphatidylcholine (PC) liposomes containing chitosan or chondroitin sulfate by the thin-film hydration method and tested for antimicrobial activity against Listeria spp. The mean particle size of PC liposomes was 145 nm and varied to 210 and 134 nm with the incorporation of chitosan and chondroitin sulfate, respectively. Nisin-containing nanovesicles with and without incorporation of polysaccharides had a zeta potential values around -20 mV, showing mostly spherical structures when observed by transmission electron microscopy. Encapsulated nisin had similar efficiency as free nisin in inhibiting Listeria spp. isolated from bovine carcass, and greater efficiency in inhibiting Listeria monocytogenes. The formulation containing chitosan was more stable and more efficient in inhibiting L. monocytogenes when compared to the other nanovesicles tested. After 24 h, the viable cell counts were 2 log lower as compared with the other treatments and 7 log comparing to controls.

  18. Crystallization of calcium oxalate monohydrate at dipalmitoylphosphatidylcholine monolayers in the presence of chondroitin sulfate A

    Science.gov (United States)

    Ouyang, Jian-Ming; Deng, Sui-Ping; Zhong, Jiu-Ping; Tieke, Bernd; Yu, Shu-Hong

    2004-10-01

    The growth and aggregation of calcium oxalate monohydrate (COM) crystals beneath dipalmitoylphosphatidylcholine (DPPC) monolayers in the presence of chondroitin sulfate A (C4S) was systematically examined under different surface pressure. The results indicated that the addition of C4S can inhibit the crystal growth and prevent the aggregation of COM crystals. Under a DPPC monolayer, well-defined three-dimensional hexagonal prisms and three-dimensional rhombus prisms with sharply angled tips were obtained. The DPPC monolayer at a surface pressure of 10 mN/m can match the Ca2+ distance of the (1 bar 0 1) face of COM better than at 20 mN/m. The addition of C4S could cooperatively modulate the interaction strength between the monolayer (or itself) with the specific morphology determining faces such as (1 bar 0 1) and (0 2 0), and thus results in remarkable stabilization of the (1 bar 0 1) faces. The dramatic changes in morphological details were due to the strong electrostatic interactions between the Ca2+-rich (1 bar 0 1) crystal faces of COM and the polyanionic polysaccharide C4S together with the negatively charged sites of the zwitterionic DPPC monolayers. The increase of the concentration of C4S can further enhance the stabilization of the (1 bar 0 1) face.

  19. Preparation and characterization of chondroitin‐sulfate‐A‐coated magnetite nanoparticles for biomedical applications

    Energy Technology Data Exchange (ETDEWEB)

    Tóth, Ildikó Y., E-mail: Ildiko.Toth@chem.u-szeged.hu; Illés, Erzsébet; Szekeres, Márta; Tombácz, Etelka, E-mail: tombacz@chem.u-szeged.hu

    2015-04-15

    Polysaccharides are promising candidates for manufacturing biocompatible core–shell nanoparticles with potential in vivo use. Superparamagnetic magnetite nanoparticles (MNPs) have prospective application in both diagnosis and therapy, and so developing a novel polysaccharide shell on MNP core is of great challenge. MNPs were prepared by co-precipitation, then the surface of purified MNPs was coated with chondroitin-sulfate-A (CSA) to obtain core–shell structured magnetite nanoparticles (CSA@MNP). The effect of the added amount of CSA on the surface charging and the aggregation state of MNPs at various pHs and 10 mM NaCl was measured by electrophoresis and dynamic light scattering. The amphoteric behavior of MNPs was fundamentally modified by adsorption of CSA polyanions. A very low CSA-loading induces the aggregation of MNPs, while four times more stabilizes the dispersions over the whole pH-range studied. The coagulation kinetics experiments measured at pH=6.3±0.3 showed that salt tolerance of CSA@MNPs rises up to ~150 mM NaCl. - Highlights: • Novel CSA-coated core–shell magnetite nanoparticles were prepared successfully. • The aggregation range of MNPs was shifted gradually to the lower pHs by CSA-loading. • CSA stabilizes electrosterically the MNPs over wide pH-range relevant to biosystems. • The salt tolerance of CSA@MNP enables them to use under physiological condition.

  20. BIO-ORGANIC CHEMISTRY QUARTERLY REPORT. March through05/1963

    Energy Technology Data Exchange (ETDEWEB)

    Various

    1963-07-23

    This report covers the following titles: (1) Fertility and litter size of normally ovulated and artificially ovulated mice; (2) Further studies on sterility produced in male mice by deuterium oxide; (3) Planarian disaggregation; (4) Uptake of organic compounds by planarians. II; (5) Effects of environmental complexity and training on acetylcholinesterase and cholinesterase activity in rat brain; (6) Effects of environmental complexity and training on brain chemistry and anatomy among mature rats; (7) Improvements in paper chromatographic techniques for labeled cell extracts; (8) measurement and adjustment of pH in small volumes of solutions; (9) Carbon-14 and Nitrogen-15 tracer studies of amino acid synthesis during photosynthesis by Chlorella Pyrenoidosa; (10) Photosynthesis of {sup 14}C-labeled protein from {sup 14}CO{sub 2} by Chlorella; (11) Further studies on carboxydismutase; (12) Electron microscopy of chlorophyll a crystals; (13) The possible role of chromanyl phosphates in oxidative and photosynthetic phosphorylation; (14) Oxidation-reductions of some coenzymes; (15) Preparation of some [{sup 14}C] labeled substances: glucose-6-phosphate, fructose-6-phosphate, 6-phosphogluconic acid, pyruvic acid, and succinic acid; (16) attempt to synthesize high molecular weight polynucleotides using Schramm's purely chemical method; and (17) Optical properties of some dye-polyanion complexes.

  1. Polyelectrolyte-Functionalized Nanofiber Mats Control the Collection and Inactivation of Escherichia coli

    Directory of Open Access Journals (Sweden)

    Katrina A. Rieger

    2016-04-01

    Full Text Available Quantifying the effect that nanofiber mat chemistry and hydrophilicity have on microorganism collection and inactivation is critical in biomedical applications. In this study, the collection and inactivation of Escherichia coli K12 was examined using cellulose nanofiber mats that were surface-functionalized using three polyelectrolytes: poly (acrylic acid (PAA, chitosan (CS, and polydiallyldimethylammonium chloride (pDADMAC. The polyelectrolyte functionalized nanofiber mats retained the cylindrical morphology and average fiber diameter (~0.84 µm of the underlying cellulose nanofibers. X-ray photoelectron spectroscopy (XPS and contact angle measurements confirmed the presence of polycations or polyanions on the surface of the nanofiber mats. Both the control cellulose and pDADMAC-functionalized nanofiber mats exhibited a high collection of E. coli K12, which suggests that mat hydrophilicity may play a larger role than surface charge on cell collection. While the minimum concentration of polycations needed to inhibit E. coli K12 was 800 µg/mL for both CS and pDADMAC, once immobilized, pDADMAC-functionalized nanofiber mats exhibited a higher inactivation of E. coli K12, (~97%. Here, we demonstrate that the collection and inactivation of microorganisms by electrospun cellulose nanofiber mats can be tailored through a facile polyelectrolyte functionalization process.

  2. Polyelectrolyte-Functionalized Nanofiber Mats Control the Collection and Inactivation of Escherichia coli

    Science.gov (United States)

    Rieger, Katrina A.; Porter, Michael; Schiffman, Jessica D.

    2016-01-01

    Quantifying the effect that nanofiber mat chemistry and hydrophilicity have on microorganism collection and inactivation is critical in biomedical applications. In this study, the collection and inactivation of Escherichia coli K12 was examined using cellulose nanofiber mats that were surface-functionalized using three polyelectrolytes: poly (acrylic acid) (PAA), chitosan (CS), and polydiallyldimethylammonium chloride (pDADMAC). The polyelectrolyte functionalized nanofiber mats retained the cylindrical morphology and average fiber diameter (~0.84 µm) of the underlying cellulose nanofibers. X-ray photoelectron spectroscopy (XPS) and contact angle measurements confirmed the presence of polycations or polyanions on the surface of the nanofiber mats. Both the control cellulose and pDADMAC-functionalized nanofiber mats exhibited a high collection of E. coli K12, which suggests that mat hydrophilicity may play a larger role than surface charge on cell collection. While the minimum concentration of polycations needed to inhibit E. coli K12 was 800 µg/mL for both CS and pDADMAC, once immobilized, pDADMAC-functionalized nanofiber mats exhibited a higher inactivation of E. coli K12, (~97%). Here, we demonstrate that the collection and inactivation of microorganisms by electrospun cellulose nanofiber mats can be tailored through a facile polyelectrolyte functionalization process. PMID:28773422

  3. pH-controlled drug loading and release from biodegradable microcapsules.

    Science.gov (United States)

    Zhao, Qinghe; Li, Bingyun

    2008-12-01

    Microcapsules made of biopolymers are of both scientific and technological interest and have many potential applications in medicine, including their use as controlled drug delivery devices. The present study makes use of the electrostatic interaction between polycations and polyanions to form a multilayered microcapsule shell and also to control the loading and release of charged drug molecules inside the microcapsule. Micron-sized calcium carbonate (CaCO3) particles were synthesized and integrated with chondroitin sulfate (CS) through a reaction between sodium carbonate and calcium nitrate tetrahydrate solutions suspended with CS macromolecules. Oppositely charged biopolymers were alternately deposited onto the synthesized particles using electrostatic layer-by-layer self-assembly, and glutaraldehyde was introduced to cross-link the multilayered shell structure. Microcapsules integrated with CS inside the multilayered shells were obtained after decomposition of the CaCO3 templates. The integration of a matrix (i.e., CS) permitted the subsequent selective control of drug loading and release. The CS-integrated microcapsules were loaded with a model drug, bovine serum albumin labeled with fluorescein isothiocyanate (FITC-BSA), and it was shown that pH was an effective means of controlling the loading and release of FITC-BSA. Such CS-integrated microcapsules may be used for controlled localized drug delivery as biodegradable devices, which have advantages in reducing systemic side effects and increasing drug efficacy.

  4. pH-Dependent Release of Insulin from Layer-by-Layer-Deposited Polyelectrolyte Microcapsules

    Directory of Open Access Journals (Sweden)

    Kentaro Yoshida

    2015-07-01

    Full Text Available Insulin-containing microcapsules were prepared by a layer-by-layer (LbL deposition of poly(allylamine hydrochloride (PAH and polyanions, such as poly(styrenesulfonate (PSS, poly(vinyl sulfate (PVS, and dextran sulfate (DS on insulin-containing calcium carbonate (CaCO3 microparticles. The CaCO3 core was dissolved in diluted HCl solution to obtain insulin-containing hollow microcapsules. The microcapsules were characterized by scanning electron microscope (SEM and atomic force microscope (AFM images and ζ-potential. The release of insulin from the microcapsules was faster at pH 9.0 and 7.4 than in acidic solutions due to the different charge density of PAH. In addition, insulin release was suppressed when the microcapsules were constructed using PAH with a lower molecular weight, probably owing to a thicker shell of the microcapsules. The results suggested a potential use of the insulin-containing microcapsules for developing insulin delivery systems.

  5. Hyaluronic Acid-Chitosan Nanoparticles to Deliver Gd-DTPA for MR Cancer Imaging

    Directory of Open Access Journals (Sweden)

    Li Zhang

    2015-08-01

    Full Text Available Molecular imaging is essential to increase the sensitivity and selectivity of cancer diagnosis especially at the early stage of tumors. Recently, polyionic nanocomplexes (PICs, which are composed of polyanions and opposite polycations, have been demonstrated to be a promising strategy for biomedical applications. In this work, chitosan-hyaluronic acid nanoparticles (GCHN were developed to deliver Gd-DTPA as MRI contrast agents for tumor diagnosis. The Gd-labeled conjugates (CS-DTPA-Gd were successfully synthesized by carbodiimide reaction, and then GCHN were prepared by ionic gelation using the obtained CS-DTPA-Gd and hyaluronic acid. The morphology of GCHN was spherical or ellipsoidal, which is observed by transmission electronic microscopy (TEM. The mean particle size and zeta potential of GCHN were 213.8 ± 2.6 nm and 19.92 ± 1.69 mV, respectively. The significant enhancement of signal intensity induced by GCHN was observed both in vitro and in vivo. Also, compared with Magnevist, GCHN was witnessed for a prolonged imaging time in the B16 tumor-bearing mice model. Furthermore, GCHN were verified as below toxic both in vitro and in vivo. These results indicated that GCHN could potentially be an alternative to current MRI contrast agents for tumor diagnosis.

  6. Layer-by-Layer Alginate and Fungal Chitosan Based Edible Coatings Applied to Fruit Bars.

    Science.gov (United States)

    Bilbao-Sainz, Cristina; Chiou, Bor-Sen; Punotai, Kaylin; Olson, Donald; Williams, Tina; Wood, Delilah; Rodov, Victor; Poverenov, Elena; McHugh, Tara

    2018-05-30

    Food waste is currently being generated at an increasing rate. One proposed solution would be to convert it to biopolymers for industrial applications. We recovered chitin from mushroom waste and converted it to chitosan to produce edible coatings. We then used layer-by-layer (LbL) electrostatic deposition of the polycation chitosan and the polyanion alginate to coat fruit bars enriched with ascorbic acid. The performance of the LbL coatings was compared with those containing single layers of fungal chitosan, animal origin chitosan and alginate. Bars containing alginate-chitosan LbL coatings showed increased ascorbic acid content, antioxidant capacity, firmness and fungal growth prevention during storage. Also, the origin of the chitosan did not affect the properties of the coatings. Mushroom stalk bases could be an alternative source for isolating chitosan with similar properties to animal-based chitosan. Also, layer-by-layer assembly is a cheap, simple method that can improve the quality and safety of fruit bars. © 2018 Institute of Food Technologists®.

  7. Ab initio identification of the Li-rich phase in LiFePO4.

    Science.gov (United States)

    Zeng, Hua; Gu, Yue; Teng, Gaofeng; Liu, Yimeng; Zheng, Jiaxin; Pan, Feng

    2018-06-27

    A recent discovery of anionic redox activity in Li-rich layered compounds opens a new direction for the design of high-capacity cathode materials for lithium-ion batteries. Here using extensive ab initio calculations, the thermodynamic existence of the Li-rich phase in LiFePO4 to form Li1+xFe1-xPO4 with x not exceeding 12.5% has been proved. Anionic redox activity and structural stability during delithiation are further investigated. Interestingly, it is found that Li1+xFe1-xPO4 cannot be delithiated completely and thus cannot achieve extra capacity by anionic redox activity, because the local oxygen-ion redox will cause the fracture of the rigid framework formed by phosphate tetrahedral polyanions. Although an extra capacity cannot be realized, the excess Li-ions at Fe sites can enhance the Li-ion diffusivity along the adjacent [010] channel and contribute to the shift from 1D to 2D/3D diffusion. This study provides a fresh perspective on olivine-type LiFePO4 and offers some important clues on designing Li-rich cathode materials with high energy density.

  8. Synthesis, structure and electronic structure of a new polymorph of CaGe2

    International Nuclear Information System (INIS)

    Tobash, Paul H.; Bobev, Svilen

    2007-01-01

    Reported are the flux synthesis, the crystal structure determination, the properties and the band structure calculations of a new polymorph of CaGe 2 , which crystallizes with the hexagonal space group P6 3 mc (no. 186) with cell parameters of a=3.9966(9) and c=10.211(4)A (Z=2; Pearson's code hP6). The structure can be viewed as puckered layers of three-bonded germanium atoms, ∼ 2 [Ge 2 ] 2- , which are stacked along the direction of the c-axis in an ABAB-fashion. The germanium polyanionic layers are separated by the Ca cations. As such, this structure is closely related to the structure of the other CaGe 2 polymorph, which crystallizes with the rhombohedral CaSi 2 type in the R3-bar m space group (No. 166), where the ∼ 2 [Ge 2 ] 2- layers are arranged in an AA'BB'CC'-fashion, and are also interspaced by Ca 2+ cations. LMTO calculations suggest that in spite of the formal closed-shell configuration for all atoms and the apparent adherence to the Zintl rules for electron counting, i.e., Ca 2+ [3b-Ge 1- ] 2 ), the phase will be a poor metal due to a small Ca-3d-Ge-4p band overlap. Magnetic susceptibility measurements as a function of the temperature indicate that the new CaGe 2 polymorph exhibits weak, temperature independent, Pauli-paramagnetism

  9. Synthesis and Materials Design for Heteroanion Compounds

    Science.gov (United States)

    Machida, K.

    2011-02-01

    Oxynitride phosphors, SrSi2O2N2:Eu2+ were synthesized through a conventional solid state reaction between Sr2SiO4:Eu2+ precursor and Si3N4 by using NH4Cl flux, and their luminescence properties were characterized from a viewpoint of the ionic and covalent bond natures as the "heteroanion compound" containing O2- and N3- anions. The structural framework of host lattice is constructed by covalently bonded layers of SiON3 units, suggesting that the rearrangement of O2- and N3- anions effectively takes place between isolated SiO44-anions of the Sr2SiO4:Eu2+ precursor and SiN4 units of the Si3N4 raw material. Furthermore, the layered structure consisting of (Si2O2N2)n2n- polyanions as tightly connected by Si-N-Si covalent bonds depresses the lattice vibration of Sr(Eu)-O or Si-O bond, so that the temperature quenching effect is lowered to give the intense emission for LED-based illumination lamps.

  10. Synthesis and Materials Design for Heteroanion Compounds

    International Nuclear Information System (INIS)

    Machida, K

    2011-01-01

    Oxynitride phosphors, SrSi 2 O 2 N 2 :Eu 2+ were synthesized through a conventional solid state reaction between Sr 2 SiO 4 :Eu 2+ precursor and Si 3 N 4 by using NH 4 Cl flux, and their luminescence properties were characterized from a viewpoint of the ionic and covalent bond natures as the 'heteroanion compound' containing O 2- and N 3- anions. The structural framework of host lattice is constructed by covalently bonded layers of SiON 3 units, suggesting that the rearrangement of O 2- and N 3- anions effectively takes place between isolated SiO4 4- anions of the Sr 2 SiO 4 :Eu 2+ precursor and SiN 4 units of the Si 3 N 4 raw material. Furthermore, the layered structure consisting of (Si 2 O 2 N 2 )n 2n- polyanions as tightly connected by Si-N-Si covalent bonds depresses the lattice vibration of Sr(Eu)-O or Si-O bond, so that the temperature quenching effect is lowered to give the intense emission for LED-based illumination lamps.

  11. Glycosaminoglycan-resistant and pH-sensitive lipid-coated DNA complexes produced by detergent removal method.

    Science.gov (United States)

    Lehtinen, Julia; Hyvönen, Zanna; Subrizi, Astrid; Bunjes, Heike; Urtti, Arto

    2008-10-21

    Cationic polymers are efficient gene delivery vectors in in vitro conditions, but these carriers can fail in vivo due to interactions with extracellular polyanions, i.e. glycosaminoglycans (GAG). The aim of this study was to develop a stable gene delivery vector that is activated at the acidic endosomal pH. Cationic DNA/PEI complexes were coated by 1,2-dioleylphosphatidylethanolamine (DOPE) and cholesteryl hemisuccinate (CHEMS) (3:2 mol/mol) using two coating methods: detergent removal and mixing with liposomes prepared by ethanol injection. Only detergent removal produced lipid-coated DNA complexes that were stable against GAGs, but were membrane active at low pH towards endosome mimicking liposomes. In relation to the low cellular uptake of the coated complexes, their transfection efficacy was relatively high. PEGylation of the coated complexes increased their cellular uptake but reduced the pH-sensitivity. Detergent removal was thus a superior method for the production of stable, but acid activatable, lipid-coated DNA complexes.

  12. Thioaluminogermanate M(AlS2)(GeS2)4 (M = Na, Ag, Cu): Synthesis, Crystal Structures, Characterization, Ion-Exchange and Solid-State 27Al and 23Na NMR Spectroscopy

    KAUST Repository

    Alahmary, Fatimah S.; Davaasuren, Bambar; Emwas, Abdul-Hamid M.; Rothenberger, Alexander

    2018-01-01

    The new thioaluminogermanate Na(AlS2)(GeS2)4 (1) was successfully synthesized by a direct combination reaction. The compound crystallizes in the monoclinic space group P21/n (no. 14) with unit cell parameters a = 6.803(3) Å, b = 38.207(2) Å, c = 6.947(4) Å, and β = 119.17(3)°. The crystal structure is composed of a [(AlS2)(GeS2)4]− 3D polyanionic network, in which Al and Ge atoms share the atomic positions and Na cations occupy the channels and voids formed by the connection of (Ge/Al)S4 tetrahedra. The title compound shows a cation-exchange property with monovalent Ag+ and Cu+ ions at room temperature in solvent media, resulting in the formation of the isostructural compounds Ag(AlS2)(GeS2)4 (2) and Cu(AlS2)(GeS2)4 (3), respectively. The ion-exchange products Ag(AlS2)(GeS2)4 (2) and Cu(AlS2)(GeS2)4 (3) show higher air stability and narrower bandgap energies compared to those of the parent compound Na(AlS2)(GeS2)4 (1).

  13. Faconnage de la surface de nanoparticules pour la delivrance de genes

    Science.gov (United States)

    Fortier, Charles

    and erythrocytes aggregation. Thus, we exposed the complementarity of several relevant interfacial characteristics for the use of polyplexes in vivo, whereby broadening our understanding of the tailoring of the surface of polyplexes with a hydrophilic polyanion. Next, we envisioned the design of a transfection agent comprising of the E/Kcoil system together with a cationic peptide (RRRRRHHHHHC or R5H5) directly grafted on a dextran backbone. This approach was developed in order to take advantage of the growing collection of Ecoil-tagged polypeptides that were being developed and characterized in our group: especially one derived from the vascular endothelial growth factor (Ecoil-VEGF), and the other from the endosomolytic peptide GALA (Ecoil-GALA). In that endeavor, two dextran-peptides conjugates were prepared and characterized: Dextran-R5H5 and Dextran-R5H5,-Kcoil. Their abilities to encapsulate DNA and to form nanoparticles were confirmed. Subsequently, in vitro transfection assays demonstrated no significant gain from controls: Dextran-R5H5 could transfect cells with no greater efficacy than that of linear PEI. We then equipped our polyplexes with Ecoil-GALA in order to facilitate endosomal escape; however we could not evidence any additional gain regarding that latter point or with respect to overall reporter gene expression. In another side study, we evaluated the utility of polyanions such as CMD in transient gene expression (TGE) for the production of r-proteins in bioreactors. We had previously observed that one of the beneficial effects of polyplex coating with CMD was related to the complexation of excess polycation, which had been linked to the cytotoxicity observed during polyplex-mediated transfection. In parallel, we confirmed that the direct use of coated polyplexes did reduce toxicity during transfection, albeit with decreased r-protein yield. We thus conjectured that the addition of polyanion after transfection could attenuate excess polycation

  14. Characterization and modelling of fluid flows in fissured and fractured media. relation with hydrothermal alterations and paleo-stress quantification; Caracterisation et modelisation des ecoulements fluides en milieu fissure. relation avec les alterations hydrothermales et quantification des paleocontraintes

    Energy Technology Data Exchange (ETDEWEB)

    Sausse, J.

    1998-10-15

    In all materials (rocks, concretes, ceramics,...), the presence of fractures at different scales implies high permeability and often oriented fluid flows. These fluid circulations in fractures induce more or less intense fluid-rock interactions with mineral crystallisation and/or dissolution. These phenomena directly depend on the nature of the fluids and the rocks, the physical and chemical properties of the media and the rate of fluid renewal (permeabilities). Usually, the development of such alterations leads to a massive sealing of the fractures (vein alterations) and of the fissures (fluid inclusion planes and microcracks, pervasive alteration). Therefore, their study brings us precious indications for the understanding of the mechanisms of fluid migrations in fossil systems. A geometrical study of the fracture systems at micro or macroscopic scales, based on the spatial distribution of sealing minerals, is applied to two different granites: the Soultz-sous-Foret granite (Bas-Rhin, France) and the Brezouard granite (Vosges, France). At the macroscopic scale, a new graphical method is proposed in order to study drilling data (Soultz granite). It allows to identify the presence of three independent mineral associations (quartz - illite, calcite-chlorite and hematite) in independent fracture systems characterised by a specific 3D geometry and hydraulic properties. These three types of vein alteration correspond to distinct and non contemporaneous fluid percolations. At the microscopic scale, the reconstitution of crack opening - fluid percolation - crack sealing stages is delicate. However, the study of their geometrical characteristics (orientations, radius, volume densities) and thereby the quantification of their porosities, exchange surfaces and permeabilities, allow to identify their respective roles in the fluid propagation. These microstructures, which are very numerous in granites, imply high but variable matrix permeabilities. This has been confirmed by

  15. Understanding the school 'climate': secondary school children and climate change

    International Nuclear Information System (INIS)

    Kovacs, Susan; Bernier, Sandrine; Blanchet, Aymeric; Derkenne, Chantal; Clement, Florence; Petitjean, Leslie

    2012-01-01

    This interdisciplinary study analyzes the production, circulation and reception of messages on climate change in secondary schools in France. The objective is to understand how political and educational policy initiatives influence the ways in which schools contribute to creating youngsters' perceptions and opinions about climate change. In order to study the conditions of production and reception of information about climate change, a survey was conducted in four French secondary schools, in the 'Bas Rhin' and 'Nord' departments, and local political actors in each department were interviewed. The cross disciplinary analytical and methodological approach uses the tools of sociological inquiry, information science, and political science: questionnaires and interviews were conducted with members of the educational and governmental communities of each school and department, semiotic and discursive analyses of corpuses of documents were carried out, in order to characterize documents used by students and teachers at school or in more informal contexts; the nature and extent of the relations between the political contexts and school directives and programs were also discussed. This interdisciplinary approach, combining sociological, communicational, and political methods, was chosen in response to the hypothesis that three types of variables (social, communicational and political) contribute to the structuring and production of messages about climate change in schools. This report offers a contextualized overview of activities developed within the four secondary schools to help sensitize children to the risks associated with climate change. A study of the networks of individuals (teachers, staff, members of associations, etc.) created in and around the school environment is presented. The degree of involvement of these actors in climate change programs is analyzed, as it is related to their motives and objectives, to the school discipline taught, and to the position

  16. Un témoin de la réception méridionale des traditions d'enseignement du Nord aux XIVe et XVe siècles : Barcelona, Biblioteca de Catalunya, M. 883

    Directory of Open Access Journals (Sweden)

    Meyer, Christian

    2003-12-01

    Full Text Available The collection of music treatises deposited at the Catalonia Library in Barcelona under the shelve-mark M. 883 gathers the main matters of the mediaeval musical education -liturgical chant, « música plana », and polyphony (organum and discantus- with the exception of the mathematical theories of the « música speculativa ». The manuscript under study transmits educational traditions spread over a geographic area located between the Seine and the Rhine : not only does the Parisian milieu is clearly discernible in it, but monastic cultures, those of the Cîteaux Order and of the Preaching Friars in particular, can also be disclosed. The contents of this collection, which may have been realised in the surroundings of the Avignon Papacy (perhaps under the Cistercian Pope Benedict XII, met with a large success in Italy during the 15th century, and show in this respect a peculiar aspect of the cultural lag there in the fields of musical practice and theory from the late 14th to the beginning of the 15th century. By 1474 in Mantua, Franchinus Gafurius drew the essential of his Tractus brevis cantus plani from this collection of treatises.[fr] Le recueil de traités de musique conservé à la Bibliothèque de Catalogne à Barcelone sous la cote M. 883 réunit les principales matières de l'enseignement de la musique -chant liturgique, "música plana" et polyphonie (organum et déchant- à l'exception des théories mathématiques de la "música speculativa". Il représente des traditions d'enseignement répandues dans une aire géographique comprise entre Seine et Rhin : le milieu parisien y occupe une place prépondérante (tradition d'enseignement de Jean de Garlande, Lambertus, mais on y distingue également des cultures monastiques, en particulier celle de l'ordre de Cîteaux et des Frères prêcheurs. Ce recueil, qui pourrait avoir été constitué à la faveur ou dans un milieu proche de la papauté d'Avignon (peut-être sous le pontificat du

  17. Sedimentary uranium deposits in France and French Union; Les gisements uraniferes dans les formations sedimentaires en France et dans l'Union francaise

    Energy Technology Data Exchange (ETDEWEB)

    Kervella, F. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1958-07-01

    The author gives the actual state of our knowledge on uranium deposits found in recent years. Till now in precambrian formations only one important deposit has been found, at Mounana (Gabon) in a series of conglomeratic sandstones belonging to the 'Francevillien'. The observed mineralization is of the uranium-vanadium type. To the carboniferous formations corresponds in France a series of deposits, among which the most important ones are located at Saint-Hippolyte. Uranium as carburans, organic-bound complexes, is contained in lacustrine schists of Westphalian or lower Stephanian formations. A number of occurrences are also known in permo-triassic formations, particularly in the Vanoise Alps, in the Maritime Alps and in the Herault, where important occurrences have recently been found not far from Lodeve. The cretaceous and tertiary systems contain uranium deposits in phosphate rocks (Morocco, Senegal, Togo, Middle-Congo). Two sedimentary oligocene deposits are known in France. Lastly, the Vinaninkarena deposit in Madagascar, known for a long time, is the only important one reported in the quaternary series. (author) [French] L'auteur fait le point des connaissances acquises sur les gisements decouverts dans les formations sedimentaires en France et dans l'Union francaise au cours des dernieres annees. Les gisements sont classes selon l'age de la formation dans laquelle on les observe. Les terrains precambriens n'ont pour l'instant fourni qu'un seul gisement notable; situe a Mouana (Gabon). C'est en decembre 1956 que cet important gisement fut decouvert dans une serie de gres conglomeratiques appartenant au Francevillien. La mineralisation observee est du type vanadium-uranium. Au carbonifere correspond en France metropolitaine une serie de gisements d'interet variable. Les plus importants sont ceux de Saint-Hippolyte (Haut-Rhin) ou l'uranium est contenu dans des schistes lacustres du Westphalien ou du

  18. Vivienda en Düsseldorf-Himmelgeist - Alemania Federal

    Directory of Open Access Journals (Sweden)

    Schneider-Esleben, P.

    1973-04-01

    Full Text Available The design of this house for a couple of scientists is outstanding, as a result of the advantages offered by the site surrounded by a river. The floors are stepped, according to their own function. The house also comprises a basement intended for services, a little swimming-pool and a sauna. On the ground floor are the entrance, drawing-room with chimney, dining-room, kitchen, studio, guests toilet, guests bedrooms, two garages, and two suites of rooms built against the main dwelling with their own entrance. A mezzanine houses a bathroom, W.C., wardrobe for the double bedroom placed just above, on the first floor, forming a tower which stands out from the lower mass of the building. The floors are vertically connected by means of spiral-stairs. Walls are made of brick, coated with white cement mortar internally and externally. Circular coloured tiles are used for dining and bathroom floors; wood floor for bedrooms; blue vitrified tiles for the swimming-pool, Rhin gravel mixed with cement mortar for the hall and chimney room; polygonal slates for the drawing-room, studio and terrace; finally, the exterior path is paved with large paving-stones arranged according to the house perimeter. Black pine wood is used for exterior carpentry. Interior wardrobes and doors are of makorée. Heating is by ducted warm air.Esta vivienda, para un matrimonio de científicos, presenta como nota dominante su diseño, resultado directo del aprovechamiento de las vistas sobre el río cercano y, en un segundo término, de la adaptación al terreno y de su contacto con él. El edificio está planteado en diferentes alturas, de acuerdo con la función que se realiza en cada planta. Semisótano con servicios, pequeña piscina interior y sauna. La entrada se realiza a nivel de la planta baja, la cual consta de: sala de estar, estancia con chimenea, comedor, cocina, pequeño estudio, aseo de invitados, cuarto de huéspedes, dos garajes, y dos apartamentos, adosados a la

  19. Synthesis and structural characterization of the ternary Zintl phases AE3Al2Pn4 and AE3Ga2Pn4 (AE=Ca, Sr, Ba, Eu; Pn=P, As)

    International Nuclear Information System (INIS)

    He, Hua; Tyson, Chauntae; Saito, Maia; Bobev, Svilen

    2012-01-01

    Ten new ternary phosphides and arsenides with empirical formulae AE 3 Al 2 Pn 4 and AE 3 Ga 2 Pn 4 (AE=Ca, Sr, Ba, Eu; Pn=P, As) have been synthesized using molten Ga, Al, and Pb fluxes. They have been structurally characterized by single-crystal and powder X-ray diffraction to form with two different structures—Ca 3 Al 2 P 4 , Sr 3 Al 2 As 4 , Eu 3 Al 2 P 4 , Eu 3 Al 2 As 4 , Ca 3 Ga 2 P 4 , Sr 3 Ga 2 P 4 , Sr 3 Ga 2 As 4 , and Eu 3 Ga 2 As 4 crystallize with the Ca 3 Al 2 As 4 structure type (space group C2/c, Z=4); Ba 3 Al 2 P 4 and Ba 3 Al 2 As 4 adopt the Na 3 Fe 2 S 4 structure type (space group Pnma, Z=4). The polyanions in both structures are made up of TrPn 4 tetrahedra, which share common corners and edges to form 2 ∞ [TrPn 2 ] 3– layers in the phases with the Ca 3 Al 2 As 4 structure, and 1 ∞ [TrPn 2 ] 3– chains in Ba 3 Al 2 P 4 and Ba 3 Al 2 As 4 with the Na 3 Fe 2 S 4 structure type. The valence electron count for all of these compounds follows the Zintl–Klemm rules. Electronic band structure calculations confirm them to be semiconductors. - Graphical abstract: AE 3 Al 2 Pn 4 and AE 3 Ga 2 Pn 4 (AE=Ca, Sr, Ba, Eu; Pn=P, As) crystallize in two different structures—Ca 3 Al 2 P 4 , Sr 3 Al 2 As 4 , Eu 3 Al 2 P 4 , Eu 3 Al 2 As 4 , Ca 3 Ga 2 P 4 , Sr 3 Ga 2 P 4 , Sr 3 Ga 2 As 4 , and Eu 3 Ga 2 As 4 , are isotypic with the previously reported Ca 3 Al 2 As 4 (space group C2/c (No. 15)), while Ba 3 Al 2 P 4 and Ba 3 Al 2 As 4 adopt a different structure known for Na 3 Fe 2 S 4 (space group Pnma (No. 62). The polyanions in both structures are made up of TrPn 4 tetrahedra, which by sharing common corners and edges, form 2 ∞ [TrPn 2 ] 3– layers in the former and 1 ∞ [TrPn 2 ] 3– chains in Ba 3 Al 2 P 4 and Ba 3 Al 2 As 4 . Highlights: ► AE 3 Ga 2 Pn 4 (AE=Ca, Sr, Ba, Eu; Pn=P, As) are new ternary pnictides. ► Ba 3 Al 2 P 4 and Ba 3 Al 2 As 4 adopt the Na 3 Fe 2 S 4 structure type. ► The Sr- and Ca-compounds crystallize with the Ca 3

  20. Ultrasensitive colorimetric detection of heparin based on self-assembly of gold nanoparticles on graphene oxide.

    Science.gov (United States)

    Fu, Xiuli; Chen, Lingxin; Li, Jinhua

    2012-08-21

    A novel colorimetric method was developed for ultrasensitive detection of heparin based on self-assembly of gold nanoparticles (AuNPs) onto the surface of graphene oxide (GO). Polycationic protamine was used as a medium for inducing the self-assembly of citrate-capped AuNPs on GO through electrostatic interaction, resulting in a shift in the surface plasmon resonance (SPR) absorption of AuNPs and exhibiting a blue color. Addition of polyanionic heparin disturbed the self-assemble of AuNPs due to its strong affinity to protamine. With the increase of heparin concentration, the amounts of self-assembly AuNPs decreased and the color changed from blue to red in solution. Therefore, a "blue-to-red" colorimetric sensing strategy based on self-assembly of AuNPs could be established for heparin detection. Compared with the commonly reported aggregation-based methods ("red-to-blue"), the color change from blue to red was more eye-sensitive, especially in low concentration of target. Moreover, stronger interaction between protamine and heparin led to distinguish heparin from its analogues as well as various potentially coexistent physiological species. The strategy was simply achieved by the self-assembly nature of AuNPs and the application of two types of polyionic media, showing it to be label-free, simple, rapid and visual. This method could selectively detect heparin with a detection limit of 3.0 ng mL(-1) in standard aqueous solution and good linearity was obtained over the range 0.06-0.36 μg mL(-1) (R = 0.9936). It was successfully applied to determination of heparin in fetal bovine serum samples as low as 1.7 ng mL(-1) with a linear range of 0-0.8 μg mL(-1).

  1. Fact versus artifact: Avoiding erroneous estimates of sulfated glycosaminoglycan content using the dimethylmethylene blue colorimetric assay for tissue-engineered constructs

    Directory of Open Access Journals (Sweden)

    CH Zheng

    2015-04-01

    Full Text Available The 1,9-dimethylmethylene blue (DMMB assay is widely used to quantify sulfated glycosaminoglycan (sGAG contents of engineered tissues, culture media, tissue samples and bodily fluids, but the assay is subject to interference from polyanions such as hyaluronic acid (HA, DNA and RNA. We examined whether specific combinations of dye pH and absorbance wavelength could minimize non-sGAG artifacts without compromising DMMB assay sensitivity. HA and DNA solutions generated substantial signal at pH 3 but not at pH 1.5. Reducing dye pH did not significantly alter sGAG measurements for normal cartilage and meniscus tissues, but eliminated anomalously high apparent sGAG contents for enzymatically isolated chondrocytes, adipose-derived stem cell (ADSC-agarose constructs and ADSC pellets. In a cartilage tissue-engineering case study, pH 3 dye indicated high apparent sGAG readings throughout culture in both basal and chondrogenic media, with a marked decline between day 14 and 21 for chondrogenic constructs. The pH 1.5 dye, however, indicated minimal sGAG accumulation in basal medium and stable sGAG content throughout culture in chondrogenic medium. As it is often difficult to know a priori whether all groups in a study will have sGAG contents high enough to overwhelm artifacts, we recommend modifying the standard DMMB assay to reduce the risk of spurious findings in tissue engineering and clinical research. Specifically, we recommend shifting to a pH 1.5 DMMB dye and basing quantification on the absorbance difference between 525 nm (µ peak and 595 nm (β peak to compensate for the moderate loss of sensitivity associated with reducing the dye pH.

  2. Historical milestones in measurement of HDL-cholesterol: impact on clinical and laboratory practice.

    Science.gov (United States)

    Langlois, Michel R; Blaton, Victor H

    2006-07-23

    High-density lipoprotein cholesterol (HDL-C) comprises a family of particles with differing physicochemical characteristics. Continuing progress in improving HDL-C analysis has originated from two separate fields-one clinical, reflecting increased attention to HDL-C in estimating risk for coronary heart disease (CHD), and the other analytical, reflecting increased emphasis on finding more reliable and cost-effective HDL-C assays. Epidemiologic and prospective studies established the inverse association of HDL-C with CHD risk, a relationship that is consistent with protective mechanisms demonstrated in basic research and animal studies. Atheroprotective and less atheroprotective HDL subpopulations have been described. Guidelines on primary and secondary CHD prevention, which increased the workload in clinical laboratories, have led to a revolution in HDL-C assay technology. Many analytical techniques including ultracentrifugation, electrophoresis, chromatography, and polyanion precipitation methods have been developed to separate and quantify HDL-C and HDL subclasses. More recently developed homogeneous assays enable direct measurement of HDL-C on an automated analyzer, without the need for manual pretreatment to separate non-HDL. Although homogeneous assays show improved accuracy and precision in normal serum, discrepant results exist in samples with atypical lipoprotein characteristics. Hypertriglyceridemia and monoclonal paraproteins are important interfering factors. A novel approach is nuclear magnetic resonance spectroscopy that allows rapid and reliable analysis of lipoprotein subclasses, which may improve the identification of individuals at increased CHD risk. Apolipoprotein A-I, the major protein of HDL, has been proposed as an alternative cardioprotective marker avoiding the analytical limitations of HDL-C.

  3. Gallic Acid Is an Antagonist of Semen Amyloid Fibrils That Enhance HIV-1 Infection*

    Science.gov (United States)

    LoRicco, Josephine G.; Xu, Changmingzi Sherry; Neidleman, Jason; Bergkvist, Magnus; Greene, Warner C.; Roan, Nadia R.; Makhatadze, George I.

    2016-01-01

    Recent in vitro studies have demonstrated that amyloid fibrils found in semen from healthy and HIV-infected men, as well as semen itself, can markedly enhance HIV infection rates. Semen fibrils are made up of multiple naturally occurring peptide fragments derived from semen. The best characterized of these fibrils are SEVI (semen-derived enhancer of viral infection), made up of residues 248–286 of prostatic acidic phosphatase, and the SEM1 fibrils, made up of residues 86–107 of semenogelin 1. A small molecule screen for antagonists of semen fibrils identified four compounds that lowered semen-mediated enhancement of HIV-1 infectivity. One of the four, gallic acid, was previously reported to antagonize other amyloids and to exert anti-inflammatory effects. To better understand the mechanism by which gallic acid modifies the properties of semen amyloids, we performed biophysical measurements (atomic force microscopy, electron microscopy, confocal microscopy, thioflavin T and Congo Red fluorescence assays, zeta potential measurements) and quantitative assays on the effects of gallic acid on semen-mediated enhancement of HIV infection and inflammation. Our results demonstrate that gallic acid binds to both SEVI and SEM1 fibrils and modifies their surface electrostatics to render them less cationic. In addition, gallic acid decreased semen-mediated enhancement of HIV infection but did not decrease the inflammatory response induced by semen. Together, these observations identify gallic acid as a non-polyanionic compound that inhibits semen-mediated enhancement of HIV infection and suggest the potential utility of incorporating gallic acid into a multicomponent microbicide targeting both the HIV virus and host components that promote viral infection. PMID:27226574

  4. Gallic Acid Is an Antagonist of Semen Amyloid Fibrils That Enhance HIV-1 Infection.

    Science.gov (United States)

    LoRicco, Josephine G; Xu, Changmingzi Sherry; Neidleman, Jason; Bergkvist, Magnus; Greene, Warner C; Roan, Nadia R; Makhatadze, George I

    2016-07-01

    Recent in vitro studies have demonstrated that amyloid fibrils found in semen from healthy and HIV-infected men, as well as semen itself, can markedly enhance HIV infection rates. Semen fibrils are made up of multiple naturally occurring peptide fragments derived from semen. The best characterized of these fibrils are SEVI (semen-derived enhancer of viral infection), made up of residues 248-286 of prostatic acidic phosphatase, and the SEM1 fibrils, made up of residues 86-107 of semenogelin 1. A small molecule screen for antagonists of semen fibrils identified four compounds that lowered semen-mediated enhancement of HIV-1 infectivity. One of the four, gallic acid, was previously reported to antagonize other amyloids and to exert anti-inflammatory effects. To better understand the mechanism by which gallic acid modifies the properties of semen amyloids, we performed biophysical measurements (atomic force microscopy, electron microscopy, confocal microscopy, thioflavin T and Congo Red fluorescence assays, zeta potential measurements) and quantitative assays on the effects of gallic acid on semen-mediated enhancement of HIV infection and inflammation. Our results demonstrate that gallic acid binds to both SEVI and SEM1 fibrils and modifies their surface electrostatics to render them less cationic. In addition, gallic acid decreased semen-mediated enhancement of HIV infection but did not decrease the inflammatory response induced by semen. Together, these observations identify gallic acid as a non-polyanionic compound that inhibits semen-mediated enhancement of HIV infection and suggest the potential utility of incorporating gallic acid into a multicomponent microbicide targeting both the HIV virus and host components that promote viral infection. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

  5. Mutation directional selection sheds light on prion pathogenesis

    Energy Technology Data Exchange (ETDEWEB)

    Shen, Liang [Shandong Provincial Research Center for Bioinformatic Engineering and Technique, Shandong University of Technology, Zibo 255049 (China); Ji, Hong-Fang, E-mail: jhf@sdut.edu.cn [Shandong Provincial Research Center for Bioinformatic Engineering and Technique, Shandong University of Technology, Zibo 255049 (China)

    2011-07-01

    Highlights: {yields} Most pathogenic mutations possess strong directional selection, i.e., enhancing hydrophobicity or decreasing negative and increasing positive charge. {yields} Mutation-induced changes may strengthen the interactions between PrP and facilitating factors. {yields} The findings also have significant implications for exploring potential regions involved in the conformational transition from PrP{sup C} to PrP{sup Sc}. -- Abstract: As mutations in the PRNP gene account for human hereditary prion diseases (PrDs), it is crucial to elucidating how these mutations affect the central pathogenic conformational transition of normal cellular prion protein (PrP{sup C}) to abnormal scrapie isoform (PrP{sup Sc}). Many studies proposed that these pathogenic mutations may make PrP more susceptible to conformational change through altering its structure stability. By evaluating the most recent observations regarding pathogenic mutations, it was found that the pathogenic mutations do not exert a uniform effect on the thermodynamic stability of the human PrP's structure. Through analyzing the reported PrDs-related mutations, we found that 25 out of 27 mutations possess strong directional selection, i.e., enhancing hydrophobicity or decreasing negative and increasing positive charge. Based on the triggering role reported by previous studies of facilitating factors in PrP{sup C} conversion, e.g., lipid and polyanion, we proposed that the mutation-induced changes may strengthen the interaction between PrP and facilitating factors, which will accelerate PrP conversion and cause PrDs.

  6. Possible indicators for low dimensional superconductivity in the quasi-1D carbide Sc{sub 3}CoC{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Scheidt, E-W; Hauf, C; Reiner, F; Eickerling, G; Scherer, W, E-mail: Ernst-Wilhelm.Scheidt@physik.uni-augsburg.de [CPM, Institut fuer Physik, Universitaet Augsburg, 86159 Augsburg (Germany)

    2011-01-01

    The transition metal carbide Sc{sub 3}CoC{sub 4} consists of a quasi-one-dimensional (1D) structure with [CoC{sub 4}]{sub {infinity}} polyanionic chains embedded in a scandium matrix. At ambient temperatures Sc{sub 3}CoC{sub 4} displays metallic behavior. At lower temperatures, however, charge density wave formation has been observed around 143 K which is followed by a structural phase transition at 72 K. Below T{sub c}{sup onset} = 4.5 K the polycrystalline sample becomes superconductive. From H{sub c1}(0) and H{sub c2}(0) values we could estimate the London penetration depth ({lambda}{sub L} {approx_equal} 9750 A) and the Ginsburg-Landau (GL) coherence length ({xi}{sub GL} {approx_equal} 187 A). The resulting GL-parameter ({kappa} {approx_equal} 52) classifies Sc{sub 3}CoC{sub 4} as a type II superconductor. Here we compare the puzzling superconducting features of Sc{sub 3}CoC{sub 4}, such as the unusual temperature dependence i) of the specific heat anomaly and ii) of the upper critical field H{sub c2}(T) at T{sub c}, and iii) the magnetic hysteresis curve, with various related low dimensional superconductors: e.g., the quasi-1D superconductor (SN){sub x} or the 2D transition-metal dichalcogenides. Our results identify Sc{sub 3}CoC{sub 4} as a new candidate for a quasi-1D superconductor.

  7. Poly(l-glutamic acid)-g-poly(ethylene glycol) external layer in polyelectrolyte multilayer films: Characterization and resistance to serum protein adsorption.

    Science.gov (United States)

    Szczepanowicz, Krzysztof; Kruk, Tomasz; Świątek, Wiktoria; Bouzga, Aud M; Simon, Christian R; Warszyński, Piotr

    2018-06-01

    Formation of protein-resistant surfaces is a major challenge in the design of novel biomaterials and an important strategy to prevent protein adsorption is the formation of protein-resistant coatings. It can be achieved by proper modification of surfaces, e.g., by immobilization of hydrophilic polymers such as poly(ethylene glycol) (PEG). An appropriate method to immobilize PEG at charged surfaces is the adsorption of copolymers with PEG chains grafted onto polyelectrolyte backbone. The growing interest in the use of polyelectrolyte multilayer coatings in biomedical applications to improve biocompatibility and/or to prepare coating with antiadhesive properties has been the main reason for these studies. Therefore the aim was to produce protein resistant polyelectrolyte multilayer films. They were formed via the layer-by-layer approach, while their pegylation by the deposition of pegylated polyanion, PGA-g-PEG, as an external layer. The influence of PEG chain length and grafting density of PGA-g-PEG copolymers on the protein antiadhesive properties of pegylated polyelectrolyte multilayer films was investigated. To monitor the formation of pegylated and non-pegylated multilayer films, adsorption of the following proteins: HSA, Fibrinogen, and FBS were measured by quartz crystal microbalance (QCM - D). We found that protein adsorption onto all pegylated polyelectrolyte multilayers was significantly reduced in comparison to non-pegylated ones. Long-term performance tests confirmed the stability and the durability of the protein resistant properties of the pegylated multilayers. Antiadhesive properties of tested surfaces pegylated by PGA-g-PEG were compared to the available data for pegylated polycation PLL-g-PEG. Copyright © 2018 Elsevier B.V. All rights reserved.

  8. New hydrogen titanium phosphate sulfate electrodes for Li-ion and Na-ion batteries

    Science.gov (United States)

    Zhao, Ran; Mieritz, Daniel; Seo, Dong-Kyun; Chan, Candace K.

    2017-03-01

    NASICON-type materials with general formula AxM2(PO4)3 (A = Li or Na, M = Ti, V, and Fe) are promising candidates for Li- and Na-ion batteries due to their open three-dimensional framework structure. Here we report the electrochemical properties of hydrogen titanium phosphate sulfate, H0.4Ti2(PO4)2.4(SO4)0.6 (HTPS), a new mixed polyanion material with NASICON structure. Micron-sized HTPS aggregates with crystallite grain size of ca. 23 nm are synthesized using a sol-gel synthesis in an acidic medium. The properties of the as-synthesized HTPS, ball-milled HTPS, and samples prepared as carbon composites using an in-situ glucose decomposition reaction are investigated. A capacity of 148 mAh g-1 corresponding to insertion of 2 Li+ per formula unit is observed in the ball-milled HTPS over the potential window of 1.5-3.4 V vs. Li/Li+. Lithiation at ca. 2.8 and 2.5 V is determined to occur through filling of the M1 and M2 sites, respectively. Powder X-ray diffraction (PXRD), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) are used characterize the HTPS before and after cycling. Evaluation of the HTPS in a Na-ion cell is also performed. A discharge capacity of 93 mAh g-1 with sodiation at ca. 2.9 and 2.2 V vs. Na/Na+ is observed.

  9. Optimization of the Use of His6-OPH-Based Enzymatic Biocatalysts for the Destruction of Chlorpyrifos in Soil

    Directory of Open Access Journals (Sweden)

    Olga Senko

    2017-11-01

    Full Text Available Applying enzymatic biocatalysts based on hexahistidine-containing organophosphorus hydrolase (His6-OPH is suggested for the decomposition of chlorpyrifos, which is actively used in agriculture in many countries. The application conditions were optimized and the following techniques was suggested to ensure the highest efficiency of the enzyme: first, the soil is alkalinized with hydrated calcitic lime Ca(OH2, then the enzyme is introduced into the soil at a concentration of 1000 U/kg soil. Non-equilibrium low temperature plasma (NELTP-modified zeolite is used for immobilization of the relatively inexpensive polyelectrolyte complexes containing the enzyme His6-OPH and a polyanionic polymer: poly-l-glutamic acid (PLE50 or poly-l-aspartic acid (PLD50. The soil’s humidity is then increased up to 60–80%, the top layer (10–30 cm of soil is thoroughly stirred, and then exposed for 48–72 h. The suggested approach ensures 100% destruction of the pesticide within 72 h in soils containing as much as 100 mg/kg of chlorpyrifos. It was concluded that using this type of His6-OPH-based enzyme chemical can be the best approach for soils with relatively low humus concentrations, such as sandy and loam-sandy chestnut soils, as well as types of soil with increased alkalinity (pH 8.0–8.4. Such soils are often encountered in desert, desert-steppe, foothills, and subtropical regions where chlorpyrifos is actively used.

  10. Glycosaminoglycan blotting on nitrocellulose membranes treated with cetylpyridinium chloride after agarose-gel electrophoretic separation.

    Science.gov (United States)

    Maccari, Francesca; Volpi, Nicola

    2002-09-01

    We describe a method for blotting and immobilizing several nonsulfated and sulfated complex polysaccharides on membranes made hydrophilic and positively charged by a cationic detergent after their separation by conventional agarose gel electrophoresis. Nitrocellulose membranes were derivatized with the cationic detergent cetylpyridinium chloride (CPC) and mixtures of glycosaminoglycans (GAGs) were capillary-blotted after their separation in agarose gel electrophoresis in barium acetate/1,2-diaminopropane. Single purified species of variously sulfated polysaccharides were transferred onto the derivatized membranes after electrophoresis with an efficiency of 100% and stained with alcian blue (irreversible staining) and toluidine blue (reversible staining) permitting about 0.1 nug threshold of detection. Nonsulfated polyanions, hyaluronic acid, a fructose-containing polysaccharide with a chondroitin backbone purified from Escherichia coli U1-41, and its defructosylated product, were also electrophoretically separated and transferred onto membranes. The limit of detection for desulfated GAGs was about 0.1-0.5 nug after irreversible or reversible staining. GAG extracts from bovine, lung and aorta, and human aorta and urine were separated by agarose gel electrophoresis and blotted on CPC-treated nitrocellulose membranes. The polysaccharide composition of these extracts was determined. The membrane stained with toluidine blue (reversible staining) was destained and the same lanes used for immunological detection or other applications. Reversible staining was also applied to recover single species of polysaccharides after electrophoretic separation of mixtures of GAGs and their transfer onto membranes. Single bands were released from the membrane with an efficiency of 70-100% for further biochemical characterization.

  11. Interactions of GRF(1-29)NH2 with plasma proteins and their effects on the release of the peptide from a PLAGA matrix.

    Science.gov (United States)

    Mariette, B; Coudane, J; Vert, M

    2005-09-02

    The administration of the GRF(1-29)NH2 Growth Hormone Releasing Hormone analog is known as relevant of the concept of drug delivery system using a bioresorbable matrix. However, the release of this peptide from poly(dl-lactic acid-co-glycolic acid) matrices is affected by its insolubility at neutral in salted media and in plasma as well. In order to investigate the origin and the nature of the insolubility in these media in more details, the precipitates collected when the peptide was set in contact with saline, isotonic pH=7.4 phosphate buffer and plasma were analyzed by various techniques, namely weighting, gel chromatography, 1D- and 2D-immunoelectrophoresis, and dialysis to discern the soluble from the insoluble or aggregated fractions. It is shown that precipitation in protein-free salted media is due to a salting out phenomenon complemented by the neutralization of the solubilizing electrostatic charges in the isotonic buffer. In contrast, the precipitation in plasma is due to inter polyelectrolyte-type complexation that involved polyanionic proteins having a rather low isoelectric point like albumin, transferin, haptoglobulin and IgG immunoglobulins. When a rather large quantity of GRF(1-29)NH2 was entrapped in bioresorbable pellets working at a percolating regime after subcutaneous implantation in rats, the peptide was slowly released despite the complexation with plasma proteins. However only a very small part of the peptide was found in blood, this small part being still large enough to cause a detectable increase of the circulating growth hormone concentration. Attempts made to increase the solubility of the peptide in plasma were successful when the peptide was combined with arginine, an amino acid known to promote the poor hormonal activity of injected GRF(1-29)NH2 solutions under clinical conditions.

  12. Characterization for Soil Fixation by Polyelectrolyte Complex

    International Nuclear Information System (INIS)

    Choi, Yong Suk; Kwon, Sang Woon; Yang, Heeman; Lee, Kune Woo; Seo, Bumkyoung; Moon, Jei Kwon

    2014-01-01

    According to report, the radioactivity bulk (approx. 95%) is localized within topsoil. Therefore soil surface on topsoil should be fixed to prevent the spreading of the contaminated soils with Cs-137 by wind and water erosion. Many methods have been developing for soil fixation to remove radioactive contaminants in soil and prevent to diffuse radioactive materials. Various materials have been also used as fixatives such as clays, molecular sieves, polymer, and petroleum based products. One of the methods is a soil fixation or solidification using polyelectrolyte. Polyelectrolytes have many ionic groups and make into the polyelectrolyte complex (PEC) due to electrostatic interaction of polyanion and polycation in an aqueous solution. It can be avoids using the chemical cross-linking agents, and reducing the possible toxicity and other undesirable effects of the reagents. PEC can fix soil particles by flocculation and formation of crust between soil. The method can also prevent a spread of radioactive material by floating on a soil surface. Recently, PEC used for the solidification of soil near the Fukushima nuclear power plant in Japan. The decontamination efficiency of the surface soils reached 90%, and dust release was effectively suppressed during the removal of surface soils. In this study, it was investigated the fixation of the soil by PEC to avoid the spread of the contamination in addition to the separation of soil and PEC. The physicochemical properties of polyelectrolyte complex solution and the stability of fixed soil by PEC were investigated. The mode of the addition is important to prepare the polyelectrolytes complex without PAA agglomerate. The concentration of salt in the polyelectrolyte complex solution is a very important parameter for the soil fixation

  13. Site-specific transition metal occupation in multicomponent pyrophosphate for improved electrochemical and thermal properties in lithium battery cathodes: a combined experimental and theoretical study.

    Science.gov (United States)

    Shakoor, Rana A; Kim, Heejin; Cho, Woosuk; Lim, Soo Yeon; Song, Hannah; Lee, Jung Woo; Kang, Jeung Ku; Kim, Yong-Tae; Jung, Yousung; Choi, Jang Wook

    2012-07-18

    As an attempt to develop lithium ion batteries with excellent performance, which is desirable for a variety of applications including mobile electronics, electrical vehicles, and utility grids, the battery community has continuously pursued cathode materials that function at higher potentials with efficient kinetics for lithium insertion and extraction. By employing both experimental and theoretical tools, herein we report multicomponent pyrophosphate (Li(2)MP(2)O(7), M = Fe(1/3)Mn(1/3)Co(1/3)) cathode materials with novel and advantageous properties as compared to the single-component analogues and other multicomponent polyanions. Li(2)Fe(1/3)Mn(1/3)Co(1/3)P(2)O(7) is formed on the basis of a solid solution among the three individual transition-metal-based pyrophosphates. The unique crystal structure of pyrophosphate and the first principles calculations show that different transition metals have a tendency to preferentially occupy either octahedral or pyramidal sites, and this site-specific transition metal occupation leads to significant improvements in various battery properties: a single-phase mode for Li insertion/extraction, improved cell potentials for Fe(2+)/Fe(3+) (raised by 0.18 eV) and Co(2+)/Co(3+) (lowered by 0.26 eV), and increased activity for Mn(2+)/Mn(3+) with significantly reduced overpotential. We reveal that the favorable energy of transition metal mixing and the sequential redox reaction for each TM element with a sufficient redox gap is the underlying physical reason for the preferential single-phase mode of Li intercalation/deintercalation reaction in pyrophosphate, a general concept that can be applied to other multicomponent systems. Furthermore, an extremely small volume change of ~0.7% between the fully charged and discharged states and the significantly enhanced thermal stability are observed for the present material, the effects unseen in previous multicomponent battery materials.

  14. Characterization for Soil Fixation by Polyelectrolyte Complex

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Yong Suk; Kwon, Sang Woon; Yang, Heeman; Lee, Kune Woo; Seo, Bumkyoung; Moon, Jei Kwon [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2014-05-15

    According to report, the radioactivity bulk (approx. 95%) is localized within topsoil. Therefore soil surface on topsoil should be fixed to prevent the spreading of the contaminated soils with Cs-137 by wind and water erosion. Many methods have been developing for soil fixation to remove radioactive contaminants in soil and prevent to diffuse radioactive materials. Various materials have been also used as fixatives such as clays, molecular sieves, polymer, and petroleum based products. One of the methods is a soil fixation or solidification using polyelectrolyte. Polyelectrolytes have many ionic groups and make into the polyelectrolyte complex (PEC) due to electrostatic interaction of polyanion and polycation in an aqueous solution. It can be avoids using the chemical cross-linking agents, and reducing the possible toxicity and other undesirable effects of the reagents. PEC can fix soil particles by flocculation and formation of crust between soil. The method can also prevent a spread of radioactive material by floating on a soil surface. Recently, PEC used for the solidification of soil near the Fukushima nuclear power plant in Japan. The decontamination efficiency of the surface soils reached 90%, and dust release was effectively suppressed during the removal of surface soils. In this study, it was investigated the fixation of the soil by PEC to avoid the spread of the contamination in addition to the separation of soil and PEC. The physicochemical properties of polyelectrolyte complex solution and the stability of fixed soil by PEC were investigated. The mode of the addition is important to prepare the polyelectrolytes complex without PAA agglomerate. The concentration of salt in the polyelectrolyte complex solution is a very important parameter for the soil fixation.

  15. Tetraphenylphosphonium iodide–1,3,5-trifluoro-2,4,6-triiodobenzene–methanol (3/4/1

    Directory of Open Access Journals (Sweden)

    Gabriella Cavallo

    2013-06-01

    Full Text Available The crystallization of a 1:1 molar solution of 1,3,5-trifluoro-2,4,6-diiodobenzene (TFTIB and tetraphenylphosponium iodide (TPPI from methanol produced tetragonal needles of pure TPPI and tabular pseudo-hexagonal truncated bipyramids of the title compound, 3C24H20P+·3I−·4C6F3I3·CH4O or (TPPI3(TFTIB4·MeOH. The asymmetric unit is composed of six TPPI molecules, eight TFTIB molecules and two methanol molecules, overall 16 constituents. The formation of the architecture is essentially guided by a number of C—I...I− halogen bonds (XB, whose lengths are in the range 3.276 (1–3.625 (1 Å. Layers of supramolecular polyanions are formed parallel to (10-1 wherein iodide anions function as penta-, tetra- or bidentate XB acceptors. The structure is not far from being P21/n, but the centrosymmetry is lost due to a different conformation of a single couple of cations and the small asymmetry in the formed supramolecular anion. One methanol molecule is hydrogen bonded to an iodide anion, while the second is linked to the first one via an O—H...O contact. This second methanol molecule is more loosely pinned in its position than the first and presents very high anisotropic displacement parameters and a seeming shortening of the C—O bond length. The crystal studied was refined as a perfect inversion twin.

  16. Factor XI Deficiency Alters the Cytokine Response and Activation of Contact Proteases during Polymicrobial Sepsis in Mice.

    Directory of Open Access Journals (Sweden)

    Charles E Bane

    Full Text Available Sepsis, a systemic inflammatory response to infection, is often accompanied by abnormalities of blood coagulation. Prior work with a mouse model of sepsis induced by cecal ligation and puncture (CLP suggested that the protease factor XIa contributed to disseminated intravascular coagulation (DIC and to the cytokine response during sepsis. We investigated the importance of factor XI to cytokine and coagulation responses during the first 24 hours after CLP. Compared to wild type littermates, factor XI-deficient (FXI-/- mice had a survival advantage after CLP, with smaller increases in plasma levels of TNF-α and IL-10 and delayed IL-1β and IL-6 responses. Plasma levels of serum amyloid P, an acute phase protein, were increased in wild type mice 24 hours post-CLP, but not in FXI-/- mice, supporting the impression of a reduced inflammatory response in the absence of factor XI. Surprisingly, there was little evidence of DIC in mice of either genotype. Plasma levels of the contact factors factor XII and prekallikrein were reduced in WT mice after CLP, consistent with induction of contact activation. However, factor XII and PK levels were not reduced in FXI-/- animals, indicating factor XI deficiency blunted contact activation. Intravenous infusion of polyphosphate into WT mice also induced changes in factor XII, but had much less effect in FXI deficient mice. In vitro analysis revealed that factor XIa activates factor XII, and that this reaction is enhanced by polyanions such polyphosphate and nucleic acids. These data suggest that factor XI deficiency confers a survival advantage in the CLP sepsis model by altering the cytokine response to infection and blunting activation of the contact (kallikrein-kinin system. The findings support the hypothesis that factor XI functions as a bidirectional interface between contact activation and thrombin generation, allowing the two processes to influence each other.

  17. Emulsion-core and polyelectrolyte-shell nanocapsules: biocompatibility and neuroprotection against SH-SY5Y cells

    International Nuclear Information System (INIS)

    Piotrowski, Marek; Szczepanowicz, Krzysztof; Jantas, Danuta; Leśkiewicz, Monika; Lasoń, Władysław; Warszyński, Piotr

    2013-01-01

    The emulsion-core and polyelectrolyte-coated nanocapsules, designed as water-insoluble neuroprotective drug delivery system, were synthesized using layer-by-layer saturation method. The isopropyl myristate was used as oil phase and docusate sodium salt as emulsifier. For the polyelectrolyte shell preparation, synthetic polyelectrolytes, cationic (PDADMAC, PAH, and PLL) and anionic (PGA) were used. The particle size and zeta potential of nanocapsules were characterized by the dynamic light scattering. The average size of synthesized nanocapsules ranged from ∼80 to ∼100 nm. Zeta potential values ranged from less than approximately −30 mV for the polyanion layers to greater than approximately +30 mV for the polycation layers. Biocompatibilities of the synthesized nanocarriers were evaluated against SH-SY5Y human neuroblastoma cells using various biochemical assays. The results obtained show that synthesized nanocapsules coated with PLL and PGA were nontoxic to SH-SY5Y cells, and they were used as nanocarriers for model neuroprotective drug (a calpain inhibitor MDL 28170). The neuroprotective action of the encapsulated MDL 28170 against hydrogen peroxide-induced oxidative stress cytotoxicity was evaluated in the same cell line. The results showed that nanoencapsulated form of MDL 28170 were biocompatible and protected SH-SY5Y cells against the H 2 O 2 (0.5 mM/24 h)-induced damage in 20–40 times lower concentrations than those of the same drug added directly to the culture medium. These data suggest that the nanoscale carriers of neuroprotective drugs might serve as novel promising therapeutic agents for oxidative stress-related neurodegenerative processes

  18. Experimental approaches to the interaction of the prion protein with nucleic acids and glycosaminoglycans: Modulators of the pathogenic conversion.

    Science.gov (United States)

    Silva, Jerson L; Vieira, Tuane C R G; Gomes, Mariana P B; Rangel, Luciana P; Scapin, Sandra M N; Cordeiro, Yraima

    2011-03-01

    The concept that transmissible spongiform encephalopathies (TSEs) are caused only by proteins has changed the traditional paradigm that disease transmission is due solely to an agent that carries genetic information. The central hypothesis for prion diseases proposes that the conversion of a cellular prion protein (PrP(C)) into a misfolded, β-sheet-rich isoform (PrP(Sc)) accounts for the development of (TSE). There is substantial evidence that the infectious material consists chiefly of a protein, PrP(Sc), with no genomic coding material, unlike a virus particle, which has both. However, prions seem to have other partners that chaperone their activities in converting the PrP(C) into the disease-causing isoform. Nucleic acids (NAs) and glycosaminoglycans (GAGs) are the most probable accomplices of prion conversion. Here, we review the recent experimental approaches that have been employed to characterize the interaction of prion proteins with nucleic acids and glycosaminoglycans. A PrP recognizes many nucleic acids and GAGs with high affinities, and this seems to be related to a pathophysiological role for this interaction. A PrP binds nucleic acids and GAGs with structural selectivity, and some PrP:NA complexes can become proteinase K-resistant, undergoing amyloid oligomerization and conversion to a β-sheet-rich structure. These results are consistent with the hypothesis that endogenous polyanions (such as NAs and GAGs) may accelerate the rate of prion disease progression by acting as scaffolds or lattices that mediate the interaction between PrP(C) and PrP(Sc) molecules. In addition to a still-possible hypothesis that nucleic acids and GAGs, especially those from the host, may modulate the conversion, the recent structural characterization of the complexes has raised the possibility of developing new diagnostic and therapeutic strategies. Copyright © 2010 Elsevier Inc. All rights reserved.

  19. Layer-by-layer films assembled from natural polymers for sustained release of neurotrophin

    International Nuclear Information System (INIS)

    Zhang, Zhiling; Li, Qianqi; Han, Lin; Zhong, Yinghui

    2015-01-01

    Cortical neural prostheses (CNPs) hold great promise for paralyzed patients by recording neural signals from the brain and translating them into movement commands. However, these electrodes normally fail to record neural signals weeks to months after implantation due to inflammation and neuronal loss around the implanted neural electrodes. Sustained local delivery of neurotrophins from biocompatible coatings on CNPs can potentially promote neuron survival and attract the nearby neurons to migrate toward the electrodes to increase neuron density at the electrode/brain interface, which is important for maintaining the recording quality and long-term performance of the implanted CNPs. However, sustained release of neurotrophins from biocompatible ultrathin coatings is very difficult to achieve. In this study, we investigated the potential of several biocompatible natural polyanions including heparin, dextran sulfate, and gelatin to form layer-by-layer (LbL) assembly with positively charged neurotrophin nerve growth factor (NGF) and its model protein lysozyme, and whether sustained release of NGF and lysozyme can be achieved from the nanoscale thin LbL coatings. We found that gelatin, which is less negatively charged than heparin and dextran sulfate, showed the highest efficacy in loading proteins into the LbL films because other interactions in addition to electrostatic interactions were involved in LbL assembly. Sustained release of NGF and lysozymes for approximately 2 weeks was achieved from the gelatin-based LbL coatings. Released NGF maintained the bioactivity to stimulate neurite outgrowth from PC12 cells. Gelatin is generally recognized as safe by the FDA. Thus, the biocompatible LbL coating developed in this study is highly promising to be used for implanted CNPs to improve their long-term performance in human patients. (paper)

  20. Copper removal using electrosterically stabilized nanocrystalline cellulose.

    Science.gov (United States)

    Sheikhi, Amir; Safari, Salman; Yang, Han; van de Ven, Theo G M

    2015-06-03

    Removal of heavy metal ions such as copper using an efficient and low-cost method with low ecological footprint is a critical process in wastewater treatment, which can be achieved in a liquid phase using nanoadsorbents such as inorganic nanoparticles. Recently, attention has turned toward developing sustainable and environmentally friendly nanoadsorbents to remove heavy metal ions from aqueous media. Electrosterically stabilized nanocrystalline cellulose (ENCC), which can be prepared from wood fibers through periodate/chlorite oxidation, has been shown to have a high charge content and colloidal stability. Here, we show that ENCC scavenges copper ions by different mechanisms depending on the ion concentration. When the Cu(II) concentration is low (C0≲200 ppm), agglomerates of starlike ENCC particles appear, which are broken into individual starlike entities by shear and Brownian motion, as evidenced by photometric dispersion analysis, dynamic light scattering, and transmission electron microscopy. On the other hand, at higher copper concentrations, the aggregate morphology changes from starlike to raftlike, which is probably due to the collapse of protruding dicarboxylic cellulose (DCC) chains and ENCC charge neutralization by copper adsorption. Such raftlike structures result from head-to-head and lateral aggregation of neutralized ENCCs as confirmed by transmission electron microscopy. As opposed to starlike aggregates, the raftlike structures grow gradually and are prone to sedimentation at copper concentrations C0≳500 ppm, which eliminates a costly separation step in wastewater treatment processes. Moreover, a copper removal capacity of ∼185 mg g(-1) was achieved thanks to the highly charged DCC polyanions protruding from ENCC. These properties along with the biorenewability make ENCC a promising candidate for wastewater treatment, in which fast, facile, and low-cost removal of heavy metal ions is desired most.

  1. Modification of nanoelectrode ensembles by thiols and disulfides to prevent non specific adsorption of proteins

    Energy Technology Data Exchange (ETDEWEB)

    Silvestrini, M. [Department of Molecular Sciences and Nanosystems, University Ca' Foscari of Venice, Santa Marta 2137, 30123 Venice (Italy); Schiavuta, P.; Scopece, P. [Associazione CIVEN, via delle Industrie 5, 30175 Marghera - Venice (Italy); Pecchielan, G.; Moretto, L.M. [Department of Molecular Sciences and Nanosystems, University Ca' Foscari of Venice, Santa Marta 2137, 30123 Venice (Italy); Ugo, P., E-mail: ugo@unive.it [Department of Molecular Sciences and Nanosystems, University Ca' Foscari of Venice, Santa Marta 2137, 30123 Venice (Italy)

    2011-09-01

    Highlights: > Complex nanostructures are built on the gold surface of ensembles of nanoelectrodes. > Gold surface of nanoelectrodes was functionalized with SAM of organic sulphurs. > The polycarbonate surrounding nanoelectrodes was functionalized with proteins. > SAMs protect the nanoelectrodes from undesired proteins adsorption. - Abstract: The possibility to functionalize selectively with thiols or disulfides the surface of the gold nanoelectrodes of polycarbonate templated nanoelectrode ensembles (NEEs) is studied. It is shown that the Au nanoelectrodes can be coated by a self assembled monolayer (SAM) of thioctic acid (TA) or 2-mercaptoethanesulfonic (MES) acid. The study of the electrochemical behavior of SAM-modified NEEs by cyclic voltammetry (CV) at different solution pH, using ferrocenecarboxylate as an anionic redox probe (FcCOO{sup -}) and (ferrocenylmethyl)trimethylammonium (FA{sup +}) as a cationic redox probe, demonstrate that the SAM-modified nanoelectrodes are permselective, in that only cationic or neutral probes can access the SAM-coated nanoelectrode surface. CV, AFM and FTIR-ATR data indicate that proteins such as casein or bovine serum albumin, which are polyanionic at pH 7, adsorb on the surface of NEEs untreated with thiols, tending to block the electron transfer of the ferrocenyl redox probes. On the contrary, the pre-treatment of the NEE with an anionic SAM protects the nanoelectrodes from protein fouling, allowing the detection of well shaped voltammetric patterns for the redox probe. Experimental results indicate that, in the case of MES treated NEEs, the protein is bound only onto the polycarbonate surface which surrounds the nanoelectrodes, while the tips of the gold nanoelectrodes remain protein free.

  2. Oxygen cathode based on a layer-by-layer self-assembled laccase and osmium redox mediator

    Energy Technology Data Exchange (ETDEWEB)

    Szamocki, R.; Flexer, V. [INQUIMAE-DQIAyQF, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, 1428 Buenos Aires (Argentina); Levin, L.; Forchiasin, F. [Micologia Experimental, Departamento de Biodiversidad y Biologia Experimental. Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, 1428 Buenos Aires (Argentina); Calvo, E.J. [INQUIMAE-DQIAyQF, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, 1428 Buenos Aires (Argentina)], E-mail: calvo@qi.fcen.uba.ar

    2009-02-28

    Trametes trogii laccase has been studied as biocatalyst for the oxygen electro-reduction in three different systems: (i) soluble laccase was studied in solution; (ii) an enzyme monolayer was tethered to a gold surface by dithiobis N-succinimidyl propionate (DTSP), with a soluble osmium pyridine-bipyridine redox mediator in both cases. The third case (iii) consisted in the sequential immobilization of laccase and the osmium complex derivatized poly(allylamine) self-assembled layer-by-layer (LbL) on mercaptopropane sulfonate modified gold to produce an all integrated and wired enzymatic oxygen cathode. The polycation was the same osmium complex covalently bound to poly-(ally-lamine) backbone (PAH-Os), the polyanion was the enzyme adsorbed from a solution of a suitable pH so that the protein carries a net negative charge. The adsorption of laccase was studied by monitoring the mass uptake with a quartz crystal microbalance and the oxygen reduction electrocatalysis was studied by linear scan voltammetry. While for the three cases, oxygen electrocatalysis mediated by the osmium complex was observed, for tethered laccase direct electron transfer in the absence of redox mediator was also apparent but no electrocatalysis for the oxygen reduction was recorded in the absence of mediator in solution. For the fully integrated LbL self-assembled laccase and redox mediator (case iii) a catalytic reduction of oxygen could be recorded at different oxygen partial pressures and different electrolyte pH. The tolerance of the reaction to methanol and chloride was also investigated.

  3. Oxygen cathode based on a layer-by-layer self-assembled laccase and osmium redox mediator

    International Nuclear Information System (INIS)

    Szamocki, R.; Flexer, V.; Levin, L.; Forchiasin, F.; Calvo, E.J.

    2009-01-01

    Trametes trogii laccase has been studied as biocatalyst for the oxygen electro-reduction in three different systems: (i) soluble laccase was studied in solution; (ii) an enzyme monolayer was tethered to a gold surface by dithiobis N-succinimidyl propionate (DTSP), with a soluble osmium pyridine-bipyridine redox mediator in both cases. The third case (iii) consisted in the sequential immobilization of laccase and the osmium complex derivatized poly(allylamine) self-assembled layer-by-layer (LbL) on mercaptopropane sulfonate modified gold to produce an all integrated and wired enzymatic oxygen cathode. The polycation was the same osmium complex covalently bound to poly-(ally-lamine) backbone (PAH-Os), the polyanion was the enzyme adsorbed from a solution of a suitable pH so that the protein carries a net negative charge. The adsorption of laccase was studied by monitoring the mass uptake with a quartz crystal microbalance and the oxygen reduction electrocatalysis was studied by linear scan voltammetry. While for the three cases, oxygen electrocatalysis mediated by the osmium complex was observed, for tethered laccase direct electron transfer in the absence of redox mediator was also apparent but no electrocatalysis for the oxygen reduction was recorded in the absence of mediator in solution. For the fully integrated LbL self-assembled laccase and redox mediator (case iii) a catalytic reduction of oxygen could be recorded at different oxygen partial pressures and different electrolyte pH. The tolerance of the reaction to methanol and chloride was also investigated

  4. Syntheses and properties of complex resins obtained by the reaction of polyethyleneimine with maleic anhydride-isobutene copolymer

    International Nuclear Information System (INIS)

    Usami, Shiro; Hasegawa, Kiyoshi; Takata, Kyoko; Naito, Ryunosuke; Uchida, Hiroshi; Kozuka, Hiroshi.

    1985-01-01

    Complex resins obtained by the reaction of polyethyleneimine with maleic anhydride-isobutene copolymer around 100 0 C revealed selective ion adsorption depending on the equivalent ratio of nitrogen to carboxyl group (N/COOH). In detail, polyanion-excess complex resins (N/COOH 2+ , Pb 2+ , Zn 2+ and Ni 2+ , and resins containing excess polycation (N/COOH > 1) for metal complex anions such as [CrO 4 ] 2- , [Ag(S 2 O 3 ) 2 ] 3- and [Fe(CN) 6 ] 4- . Furthermore, the polycation-excess complex resins had high adsorption capacity for uranium in solution, for example, a polycationic resin (N/COOH = 1.79) had an adsorption capacity of more than 100 mg U/g-dry base resin in a 75 ppm uranium solution. It also adsorbed and recovered uranium from solution contatining such infinitesimal amounts of uranium as sea water. The results from electron probe X-ray microanalyser (EPMA) of a polycationic resin (N/COOH = 1.79) indicated that cations such as Ca 2+ and Mg 2+ , abundant in sea water, were not adsorbed at all while such anions as Cl - and S 2- were adsorbed. It was found that Br - , I - , etc. were not adsorbed from sea water while these anions were adsorbed from the solutions containing them independently. The result indicated that Cl - in sea water probably interfered the adsorption of Br - , I - , etc. However, uranium was adsorbed from sea water in spite of its extremely low concentration without any disturbance of other co-existing ions. It was found that Ni 2+ and Cu 2+ were also adsorbed. (author)

  5. Interaction of a common painkiller piroxicam and copper-piroxicam with chromatin causes structural alterations accompanied by modulation at the epigenomic/genomic level.

    Science.gov (United States)

    Goswami, Sathi; Sanyal, Sulagna; Chakraborty, Payal; Das, Chandrima; Sarkar, Munna

    2017-08-01

    NSAIDs are the most common class of painkillers and anti-inflammatory agents. They also show other functions like chemoprevention and chemosuppression for which they act at the protein but not at the genome level since they are mostly anions at physiological pH, which prohibit their approach to the poly-anionic DNA. Complexing the drugs with bioactive metal obliterate their negative charge and allow them to bind to the DNA, thereby, opening the possibility of genome level interaction. To test this hypothesis, we present the interaction of a traditional NSAID, Piroxicam and its copper complex with core histone and chromatin. Spectroscopy, DLS, and SEM studies were applied to see the effect of the interaction on the structure of histone/chromatin. This was coupled with MTT assay, immunoblot analysis, confocal microscopy, micro array analysis and qRT-PCR. The interaction of Piroxicam and its copper complex with histone/chromatin results in structural alterations. Such structural alterations can have different biological manifestations, but to test our hypothesis, we have focused only on the accompanied modulations at the epigenomic/genomic level. The complex, showed alteration of key epigenetic signatures implicated in transcription in the global context, although Piroxicam caused no significant changes. We have correlated such alterations caused by the complex with the changes in global gene expression and validated the candidate gene expression alterations. Our results provide the proof of concept that DNA binding ability of the copper complexes of a traditional NSAID, opens up the possibility of modulations at the epigenomic/genomic level. Copyright © 2017 Elsevier B.V. All rights reserved.

  6. Artificial cartilage bio-matrix formed of hyaluronic acid and Mg2+-polyphosphate

    Directory of Open Access Journals (Sweden)

    X Wang

    2016-11-01

    Full Text Available Here we show that inorganic polyphosphate (polyP, a polyanionic metabolic regulator consisting of multiple phosphate residues linked by energy-rich phosphoanhydride bonds, is present in the synovial fluid. In a biomimetic approach, to enhance cartilage synthesis and regeneration, we prepared amorphous polyP microparticles with Mg2+ as counterions. The particles were characterised by X-ray diffraction (XRD, energy-dispersive X-ray (EDX and Fourier transformed infrared spectroscopic (FTIR analyses. Similar particles were obtained after addition of Mg2+ ions to a solution containing hyaluronic acid, as a major component of the synovial fluid, and soluble Na-polyP. The viscous paste-like material formed, composed of globular microparticles with diameter of 400 nm, strongly promoted the adhesion of chondrocytes and caused a significant upregulation of the expression of the genes encoding collagen type 3A1, as a marker for chondrocyte differentiation, and SOX9, a transcription factor that regulates chondrocyte differentiation and proliferation. The expression level of the collagen type 3A1 gene was also enhanced by exposure of chondrocytes to synovial fluid that was found to contain polyP with a size of about 80 phosphate residues. This stimulatory effect was abolished after pre-incubation of the synovial fluid with the polyP degrading alkaline phosphatase. We propose a strategy for treatment of joint dysfunctions caused by osteoarthritis based on the application of amorphous Mg2+-polyP microparticles thatprevent calcium crystal formation in the synovial fluid using scavenging Ca2+ ions (Mg2+/Ca2+ exchange and enhance chondrocyte function after binding of the Ca2+-polyP to hyaluronic acid at the cartilage surface.

  7. Smart systems related to polypeptide sequences

    Directory of Open Access Journals (Sweden)

    Lourdes Franco

    2016-03-01

    Full Text Available Increasing interest for the application of polypeptide-based smart systems in the biomedical field has developed due to the advantages given by the peptidic sequence. This is due to characteristics of these systems, which include: biocompatibility, potential control of degradation, capability to provide a rich repertoire of biologically specific interactions, feasibility to self-assemble, possibility to combine different functionalities, and capability to give an environmentally responsive behavior. Recently, applications concerning the development of these systems are receiving greater attention since a targeted and programmable release of drugs (e.g. anti-cancer agents can be achieved. Block copolymers are discussed due to their capability to render differently assembled architectures. Hybrid systems based on silica nanoparticles are also discussed. In both cases, the selected systems must be able to undergo fast changes in properties like solubility, shape, and dissociation or swelling capabilities. This review is structured in different chapters which explain the most recent advances on smart systems depending on the stimuli to which they are sensitive. Amphiphilic block copolymers based on polyanionic or polycationic peptides are, for example, typically employed for obtaining pH-responsive systems. Elastin-like polypeptides are usually used as thermoresponsive polymers, but performance can be increased by using techniques which utilize layer-by-layer electrostatic self-assembly. This approach offers a great potential to create multilayered systems, including nanocapsules, with different functionality. Recent strategies developed to get redox-, magnetic-, ultrasound-, enzyme-, light- and electric-responsive systems are extensively discussed. Finally, some indications concerning the possibilities of multi-responsive systems are discussed.

  8. The quaternary arsenide oxides Ce{sub 9}Au{sub 5-x}As{sub 8}O{sub 6} and Pr{sub 9}Au{sub 5-x}As{sub 8}O{sub 6}

    Energy Technology Data Exchange (ETDEWEB)

    Bartsch, Timo; Hoffmann, Rolf-Dieter; Poettgen, Rainer [Univ. Muenster (Germany). Inst. fuer Anorganische und Analytische Chemie

    2016-07-01

    The quaternary gold arsenide oxides Ce{sub 9}Au{sub 5-x}As{sub 8}O{sub 6} and Pr{sub 9}Au{sub 5-x}As{sub 8}O{sub 6} were synthesized from the rare earth elements (RE), rare earth oxides, arsenic and gold powder at maximum annealing temperatures of 1173 K. The structures were refined from single crystal X-ray diffractometer data: Pnnm, a=1321.64(6) pm, b=4073.0(3), c=423.96(2), wR2=0.0842, 3106 F{sup 2} values, 160 variables for Ce{sub 9}Au{sub 4.91(4)}As{sub 8}O{sub 6} and Pnnm, a=1315.01(4), b=4052.87(8), c=420.68(1) pm, wR2=0.0865, 5313 F{sup 2} values, 160 variables for Pr{sub 9}Au{sub 4.75(1)}As{sub 8}O{sub 6}. They represent a new structure type and show a further extension of pnictide oxide crystal chemistry. A complex polyanionic gold arsenide network [Au{sub 5}As{sub 8}]{sup 15-} (with some disorder in the gold substructure) is charge compensated with polycationic strands of condensed edge-sharing O rate at RE{sub 4/4} and O rate at RE{sub 4/3} tetrahedra ([RE{sub 4}O{sub 3}]{sub 2}{sup 12+}) as well as RE{sup 3+} cations in cavities.

  9. Polyelectrolyte-coated nanocapsules containing undecylenic acid: Synthesis, biocompatibility and neuroprotective properties.

    Science.gov (United States)

    Piotrowski, Marek; Jantas, Danuta; Szczepanowicz, Krzysztof; Łukasiewicz, Sylwia; Lasoń, Władysław; Warszyński, Piotr

    2015-11-01

    The main objectives of the present study were to investigate the biocompatibility of polyelectrolyte-coated nanocapsules and to evaluate the neuroprotective action of the nanoencapsulated water-insoluble neuroprotective drug-undecylenic acid (UDA), in vitro. Core-shell nanocapsules were synthesized using nanoemulsification and the layer-by-layer (LbL) technique (by saturation method). The average size of synthesized nanocapsules was around 80 nm and the concentration was 2.5 × 10(10) particles/ml. Their zeta potential values ranged from less than -30 mV for the ones with external polyanion layers through -4 mV for the PEG-ylated layers to more than 30 mV for the polycation layers. Biocompatibility of synthesized nanocarriers was evaluated in the SH-SY5Y human neuroblastoma cell line using cell viability/toxicity assays (MTT reduction, LDH release). The results obtained showed that synthesized nanocapsules coated with PLL and PGA (also PEG-ylated) were non-toxic to SH-SY5Y cells, therefore, they were used as nanocarriers for UDA. Moreover, studies with ROD/FITC-labeled polyelectrolytes demonstrated approximately 20% cellular uptake of synthetized nanocapsules. Further studies showed that nanoencapsulated form of UDA was biocompatible and protected SH-SY5Y cells against the staurosporine-induced damage in lower concentrations than those of the same drug added directly to the culture medium. These data suggest that designed nanocapsules might serve as novel, promising delivery systems for neuroprotective agents. Copyright © 2015 Elsevier B.V. All rights reserved.

  10. Organic-inorganic hybrid supramolecular assemblies based on isomers [H{sub x}As{sub 2}Mo{sub 6}O{sub 26}]{sup (6-x)-} clusters

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Zhi-Feng [College of Material Science and Engineering, Heilongjiang University of Science and Technology, Harbin (China); Su, Zhan-Hua; Cong, Bo-Wen; Zhao, Wen-Qi; Ma, Xiu-Juan [School of Chemistry and Chemical Engineering, Harbin Normal University, Harbin (China)

    2017-08-16

    The arsenomolybdates [H{sub 2}As{sub 2}Mo{sub 6}O{sub 26}(H{sub 2}O)].(H{sub 2}biyb){sub 2}.2H{sub 2}O (1) and [H{sub 3}As{sub 2}Mo{sub 6}O{sub 26}].(H{sub 3}pt){sub 2} (2) [biyb = 1,4-bis(imidazol-1-ylmethyl)benzene, pt = 4'-(3{sup ''}-pyridyl)-2,3':6'3{sup ''}-terpyridine] were synthesized via hydrothermal method. The structures of the compounds were characterized by single-crystal X-ray diffraction analyses, elemental analyses, IR spectroscopy, and TG analysis. Compounds 1 and 2 exhibit two isomeric forms of [H{sub x}As{sub 2}Mo{sub 6}O{sub 26}]{sup (6-x)-}. The structure of 1 is constructed from the B-type [H{sub 2}As{sub 2}Mo{sub 6}O{sub 26}(H{sub 2}O)]{sup 4-} polyanions and free biyb ligands via weak interactions to form 3D supramolecular framework with a {3.4.5"3.6}{3.4"3.5"2}{3.5.6}{sup 2}{3.5"2}{sup 2} topology structure. In compound 2, the A-type [H{sub 3}As{sub 2}Mo{sub 6}O{sub 26}]{sup 3-} clusters are surrounded by pt ligands through hydrogen bond interactions forming 3D supramolecular framework with a {4"3.6"3}{sup 2}{4"6.6"6.8"3} topology structure. The electrochemical behaviors, electrocatalytic and photocatalytic activities of 1 and 2 are detected. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  11. Thermodynamics of kappa-Carrageenan-Amphiphilic Drug Interaction as Influenced by Specific Counterions and Temperature: A Microcalorimetric and Viscometric Study.

    Science.gov (United States)

    Singh; Caram-Lelham

    1998-07-15

    The adsorption of amphiphilic drug molecules to a polyelectrolyte, kappa-carrageenan, has been shown to be related to hydrophobicity of drug and the conformation of the polyanion which in turn can be regulated by choice of counterion. The binding is of a strongly cooperative nature and the degree of cooperativity has been found to be related to the self-aggregation tendency of the drug molecules. This system has been examined by titration microcalorimetry and capillary viscometry to determine the thermodynamics of the binding phenomenon. The titration calorimetry data confirms the trends and conclusions drawn regarding the factors that control the binding. Viscometry shows that although there is a change in size of the polymeric chains when the drug molecules are adsorbed, the effect is primarily due to charge neutralization and not a conformation change. This allows the microcalorimetry data to be analyzed to recover the enthalpy of binding of the drug molecules to the polymer. Earlier published equilibrium binding data has been analyzed to determine the binding constants and free energy changes in the process (-25 to -90 kJ/mol). A phenomenological model has been derived for the cooperative binding process for this purpose. The binding process is primarily enthalpy driven with the major part of enthalpy change (-10 to -40 kJ/mol) arising from the aggregation of bound drug molecules, i.e., from hydrophobic interactions; the process is also entropically favorable. The size of these aggregates in polymer-bound state is of the order of 2-5 molecules of drug, similar to the pre-micellar aggregates of the drugs in solution. Copyright 1998 Academic Press.

  12. Charge neutralization as the major factor for the assembly of nucleocapsid-like particles from C-terminal truncated hepatitis C virus core protein.

    Science.gov (United States)

    de Souza, Theo Luiz Ferraz; de Lima, Sheila Maria Barbosa; Braga, Vanessa L de Azevedo; Peabody, David S; Ferreira, Davis Fernandes; Bianconi, M Lucia; Gomes, Andre Marco de Oliveira; Silva, Jerson Lima; de Oliveira, Andréa Cheble

    2016-01-01

    Hepatitis C virus (HCV) core protein, in addition to its structural role to form the nucleocapsid assembly, plays a critical role in HCV pathogenesis by interfering in several cellular processes, including microRNA and mRNA homeostasis. The C-terminal truncated HCV core protein (C124) is intrinsically unstructured in solution and is able to interact with unspecific nucleic acids, in the micromolar range, and to assemble into nucleocapsid-like particles (NLPs) in vitro . The specificity and propensity of C124 to the assembly and its implications on HCV pathogenesis are not well understood. Spectroscopic techniques, transmission electron microscopy and calorimetry were used to better understand the propensity of C124 to fold or to multimerize into NLPs when subjected to different conditions or in the presence of unspecific nucleic acids of equivalent size to cellular microRNAs. The structural analysis indicated that C124 has low propensity to self-folding. On the other hand, for the first time, we show that C124, in the absence of nucleic acids, multimerizes into empty NLPs when subjected to a pH close to its isoelectric point (pH ≈ 12), indicating that assembly is mainly driven by charge neutralization. Isothermal calorimetry data showed that the assembly of NLPs promoted by nucleic acids is enthalpy driven. Additionally, data obtained from fluorescence correlation spectroscopy show that C124, in nanomolar range, was able to interact and to sequester a large number of short unspecific nucleic acids into NLPs. Together, our data showed that the charge neutralization is the major factor for the nucleocapsid-like particles assembly from C-terminal truncated HCV core protein. This finding suggests that HCV core protein may physically interact with unspecific cellular polyanions, which may correspond to microRNAs and mRNAs in a host cell infected by HCV, triggering their confinement into infectious particles.

  13. Syntheses, crystal structures and solid-state properties of the lanthanoid-containing nanoclusters [(Ln{sub 2}PW{sub 10}O{sub 38}){sub 4}(W{sub 3}O{sub 8})(OH){sub 4}(H{sub 2}O){sub 2}]{sup 26-}

    Energy Technology Data Exchange (ETDEWEB)

    Gupta, Rakesh; Saini, Mukesh Kumar; Hussain, Firasat [Department of Chemistry, University of Delhi (India)

    2014-12-15

    A series of lanthanoid-substituted polyoxometalates have been synthesized by a self-assembly process in potassium chloride solution by the reaction of dilacunary [P{sub 2}W{sub 19}O{sub 69}(H{sub 2}O)]{sup 14-} with mid- and late-lanthanoid Ln(NO{sub 3}){sub 3}.nH{sub 2}O salts leading to the formation of the tetrameric tungstophosphates [(Ln{sub 2}PW{sub 10}O{sub 38}){sub 4}(W{sub 3}O{sub 8})(OH){sub 4}(H{sub 2}O){sub 2}]{sup 26-} [Ln = Y{sup 3+} (1), Sm{sup 3+} (2), Eu{sup 3+} (3), Gd{sup 3+} (4), Tb{sup 3+} (5), Dy{sup 3+} (6), Ho{sup 3+} (7), Er{sup 3+} (8), Tm{sup 3+} (9), Yb{sup 3+} (10)]. The polyanions were isolated as potassium or mixed-alkali salts. Most of the compounds were characterized by single-crystal X-ray diffraction and various analytical techniques, such as FTIR, UV/Vis, {sup 31}P NMR and photoluminescence spectroscopy, magnetism, as well as thermogravimetric analysis. The FTIR spectra suggest that all the compounds are isomorphous. The crystal structures of these complexes consist of four A-[α-PW{sub 10}O{sub 36}]{sup 7-} units, each incorporating two Ln{sup III} ions to create four Keggin-like anions that further assemble with three additional tungstate units to form a tetramer species with C{sub 2} symmetry. The photoluminescent properties of 3a and 6a were investigated following photoexcitation at room temperature. The magnetic properties of 3a, 4a, 5a and 6a were investigated at room temperature, the complexes exhibiting paramagnetic behaviour. (Copyright copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  14. Synthesis and Characterization of the Rubidium Thiophosphate Rb 6 (PS 5 )(P 2 S 10 ) and the Rubidium Silver Thiophosphates Rb 2 AgPS 4 , RbAg 5 (PS 4 ) 2 and Rb 3 Ag 9 (PS 4 ) 4

    KAUST Repository

    Alahmary, Fatimah S.

    2016-02-18

    The metal thiophosphates Rb2AgPS4 (2), RbAg5(PS4)2 (3), and Rb3Ag9(PS4)4 (4) were synthesized by stoichiometric reactions, whereas Rb6(PS5)(P2S10) (1) was prepared with excess amount of sulfur. The compounds crystallize as follows: 1 monoclinic, P21/c (no. 14), a = 17.0123(7) Å, b = 6.9102(2) Å, c = 23.179(1) Å, β = 94.399(4)°; 2 triclinic, P ¯ (no. 2), a = 6.600(1) Å, b = 6.856(1) Å, c = 10.943(3) Å, α = 95.150(2)°, β = 107.338(2)°, γ = 111.383(2)°; 3 orthorhombic, Pbca (no. 61), a = 12.607(1) Å, b = 12.612(1) Å, c = 17.759(2) Å; 4 orthorhombic, Pbcm (no. 57), a = 6.3481(2) Å, b = 12.5782(4) Å, c = 35.975(1) Å. The crystal structures contain discrete units, chains, and 3D polyanionic frameworks composed of PS4 tetrahedral units arranged and connected in different manner. Compounds 1-3 melt congruently, whereas incongruent melting behavior was observed for compound 4. 1-4 are semiconductors with bandgaps between 2.3 and 2.6 eV and thermally stable up to 450 °C in an inert atmosphere. Copyright © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Neutralization of Apis mellifera bee venom activities by suramin.

    Science.gov (United States)

    El-Kik, Camila Z; Fernandes, Fabrício F A; Tomaz, Marcelo Amorim; Gaban, Glauco A; Fonseca, Tatiane F; Calil-Elias, Sabrina; Oliveira, Suellen D S; Silva, Claudia L M; Martinez, Ana Maria Blanco; Melo, Paulo A

    2013-06-01

    In this work we evaluated the ability of suramin, a polysulfonated naphthylurea derivative, to antagonize the cytotoxic and enzymatic effects of the crude venom of Apis mellifera. Suramin was efficient to decrease the lethality in a dose-dependent way. The hemoconcentration caused by lethal dose injection of bee venom was abolished by suramin (30 μg/g). The edematogenic activity of the venom (0.3 μg/g) was antagonized by suramin (10 μg/g) in all treatment protocols. The changes in the vascular permeability caused by A. mellifera (1 μg/g) venom were inhibited by suramin (30 μg/g) in the pre- and posttreatment as well as when the venom was preincubated with suramin. In addition, suramin also inhibited cultured endothelial cell lesion, as well as in vitro myotoxicity, evaluated in mouse extensor digitorum longus muscle, which was inhibited by suramin (10 and 25 μM), decreasing the rate of CK release, showing that suramin protected the sarcolemma against damage induced by components of bee venom (2.5 μg/mL). Moreover, suramin inhibited the in vivo myotoxicity induced by i.m. injection of A. mellifera venom in mice (0.5 μg/g). The analysis of the area under the plasma CK vs. time curve showed that preincubation, pre- and posttreatment with suramin (30 μg/g) inhibited bee venom myotoxic activity in mice by about 89%, 45% and 40%, respectively. Suramin markedly inhibited the PLA2 activity in a concentration-dependent way (1-30 μM). Being suramin a polyanion molecule, the effects observed may be due to the interaction of its charges with the polycation components present in A. mellifera bee venom. Copyright © 2013 Elsevier Ltd. All rights reserved.

  16. Porphyrin-functionalized porous polysulfone membrane towards an optical sensor membrane for sorption and detection of cadmium(II)

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Lizhi, E-mail: zhaolizhi_phd@163.com [State Key Laboratory of Separation Membranes and Membrane Processes, School of Materials Science and Engineering, Tianjin Polytechnic University, Tianjin 300387 (China); Li, Min; Liu, Manman; Zhang, Yuecong [State Key Laboratory of Separation Membranes and Membrane Processes, School of Materials Science and Engineering, Tianjin Polytechnic University, Tianjin 300387 (China); Wu, Chenglin [School of Pharmaceutical and Chemical Engineering, Taizhou University, Taizhou 317000, Zhejiang Province (China); Zhang, Yuzhong, E-mail: zhangyz2004cn@163.com [State Key Laboratory of Separation Membranes and Membrane Processes, School of Materials Science and Engineering, Tianjin Polytechnic University, Tianjin 300387 (China)

    2016-01-15

    Highlights: • An optical sensor membrane is prepared by TMPyP and PNaSS-grafted PSF membrane. • The optical sensor membrane shows enhanced sorption for cadmium(II). • Visual and spectrophotometric detection can be achieved. • The functional membrane exhibits good stability and reusability. - Abstract: In this study, an optical sensor membrane was prepared for sorption and detection of cadmium(II) (Cd(II)) in aqueous solution. A polyanion, poly(sodium 4-styrenesulfonate) (PNaSS), was grafted onto the chloromethylated polysulfone (CMPSF) microporous membrane via surface-initiated ATRP. 5,10,15,20-tetrakis(4-N-methylpyridyl) porphyrin p-toluenesulfonate (TMPyP) was immobilized onto the PNaSS-grafted polysulfone (PSF-PNaSS) membrane through electrostatic interaction. The TMPyP-functionalized membrane exhibited an enhanced sorption for, and distinct color and spectral response to cadmium(II) (Cd(II)) in aqueous solution. Larger immobilization capacity of TMPyP on the membrane led to stronger sorption for Cd(II), and smaller one made the optical sensor have a faster (in minutes) and more sensitive response to the ion. The detection limit study indicated that the functional membrane with proper amount of TMPyP (<0.5 mg/g) could still have color and spectral response to Cd(II) solutions at an extreme low concentration (10{sup −4} mg/L). The optical sensor membrane exhibited good stability and reusability which made it efficient for various sorptive removal and detection applications.

  17. Modelling of proton and metal exchange in the alginate biopolymer.

    Science.gov (United States)

    De Stefano, Concetta; Gianguzza, Antonio; Piazzese, Daniela; Sammartano, Silvio

    2005-10-01

    Acid-base behaviour of a commercial sodium alginate extracted from brown seaweed (Macrocystis pyrifera) has been investigated at different ionic strengths (0.1titration calorimetric data were expressed as a function of the dissociation degree (alpha) using different models (Henderson-Hasselbalch modified, Högfeldt three parameters and linear equations). The dependence on ionic strength of the protonation constants was taken into account by a modified specific interaction theory model. Differences among different media were explained in terms of the interaction between polyanion and metal cations of the supporting electrolytes. Quantitative information on the proton-binding capacity, together with the stabilities of different species formed, is reported. Protonation thermodynamic parameters, at alpha=0.5, are log K H=3.686+/-0.005, DeltaG 0=-21.04+/-0.03 kJ mol(-1), DeltaH 0=4.8+/-0.2 kJ mol(-1) and TDeltaS 0=35.7+/-0.3 kJ mol(-1), at infinite dilution. Protonation enthalpies indicate that the main contribution to proton binding arises from the entropy term. A strict correlation between DeltaG and TDeltaS was found, TDeltaS=-9.5-1.73 DeltaG. Results are reported in light of building up a chemical complexation model of general validity to explain the binding ability of naturally occurring polycarboxylate polymers and biopolymers. Speciation profiles of alginate in the presence of sodium and magnesium ions, naturally occurring cations in natural waters, are also reported.

  18. Clinical use of vaginal or rectally applied microbicides in patients suffering from HIV/AIDS.

    Science.gov (United States)

    Gupta, Satish Kumar; Nutan

    2013-10-22

    Microbicides, primarily used as topical pre-exposure prophylaxis, have been proposed to prevent sexual transmission of HIV. This review covers the trends and challenges in the development of safe and effective microbicides to prevent sexual transmission of HIV Initial phases of microbicide development used such surfactants as nonoxynol-9 (N-9), C13G, and sodium lauryl sulfate, aiming to inactivate the virus. Clinical trials of microbicides based on N-9 and C31G failed to inhibit sexual transmission of HIV. On the contrary, N-9 enhanced susceptibility to sexual transmission of HIV-1. Subsequently, microbicides based on polyanions and a variety of other compounds that inhibit the binding, fusion, or entry of virus to the host cells were evaluated for their efficacy in different clinical setups. Most of these trials failed to show either safety or efficacy for prevention of HIV transmission. The next phase of microbicide development involved antiretroviral drugs. Microbicide in the form of 1% tenofovir vaginal gel when tested in a Phase IIb trial (CAPRISA 004) in a coitally dependent manner revealed that tenofovir gel users were 39% less likely to become HIV-infected compared to placebo control. However, in another trial (VOICE MTN 003), tenofovir gel used once daily in a coitally independent mode failed to show any efficacy to prevent HIV infection. Tenofovir gel is currently in a Phase III safety and efficacy trial in South Africa (FACTS 001) employing a coitally dependent dosing regimen. Further, long-acting microbicide-delivery systems (vaginal ring) for slow release of such antiretroviral drugs as dapivirine are also undergoing clinical trials. Discovering new markers as correlates of protective efficacy, novel long-acting delivery systems with improved adherence in the use of microbicides, discovering new compounds effective against a broad spectrum of HIV strains, developing multipurpose technologies incorporating additional features of efficacy against other

  19. Separation of metallic cations by means of coupled filtration on a ceramic membrane. Use of a complexing heteropolyanion

    International Nuclear Information System (INIS)

    Brun, Stephane

    1999-01-01

    In the field of the high level nuclear waste reprocessing, the Nuclear French Agency is currently carrying out studies on several processes (including the SESAME process) which aim at separating radioactive elements in order to dispose them specifically or to transmute them. One of these processes concerns the selective extraction of americium at an upper oxidation state than Ill. This work deals with the separation of Am(IV) from Ln(Ill) by means of complexation-coupled tangential filtration on alumina-titanium ceramic membranes. The chosen selective complexing agent is a lacunar heteropolyanion from the tungstophosphate family α_2P_2W_1_7O_6_1"1"0"-, which synthesis and various properties in solution have been studied. The polyanion stability in 0.5 M nitric solution strongly depends on the quality of the synthesised product. Two analytical techniques were developed to check the quality of the synthesised sets: "3"1P NMR and arsenazo-lanthanum complexometric titration. The separation studies on the cerium (IV)-neodymium (Ill) system were carried out to simulate americium(IV)/lanthanides(Ill) system. For the two alumina-titanium membranes studied (ultrafiltration and nano-filtration), the solvent flow can be described through a capillary mechanism which is characteristic of porous membranes. The ion transfer through the membranes, mainly governed by electrostatic interactions, strongly depends on the ionic strength at the membrane-solution interface. The best separation results, using nano-filtration, still remain below the expected performances, with a Ce(IV)/Nd(Ill) separation factor of 35 on a single stage in 0,5 M nitric medium. (author) [fr

  20. A transgenic rat hepatocyte - Kupffer cell co-culture model for evaluation of direct and macrophage-related effect of poly(amidoamine) dendrimers.

    Science.gov (United States)

    Jemnitz, Katalin; Bátai-Konczos, Attila; Szabó, Mónika; Ioja, Enikő; Kolacsek, Orsolya; Orbán, Tamás I; Török, György; Homolya, László; Kovács, Eszter; Jablonkai, István; Veres, Zsuzsa

    2017-02-01

    Increasing number of papers demonstrate that Kupffer cells (KCs) play a role in the development of drug induced liver injury (DILI). Furthermore, elevated intracellular Ca 2+ level of hepatocytes is considered as a common marker of DILI. Here we applied an in vitro model based on hepatocyte mono- and hepatocyte/KC co-cultures (H/KC) isolated from transgenic rats stably expressing the GCaMP2 fluorescent Ca 2+ sensor protein to investigate the effects of polycationic (G5), polyanionic (G4.5) and polyethylene-glycol coated neutral (G5 Peg) dendrimers known to accumulate in the liver, primarily in KCs. Following dendrimer exposure, hepatocyte homeostasis was measured by MTT cytotoxicity assay and by Ca 2+ imaging, while hepatocyte functions were studied by CYP2B1/2 inducibility, and bilirubin and taurocholate transport. G5 was significantly more cytotoxic than G4.5 for hepatocytes and induced Ca 2+ oscillation and sustained Ca 2+ signals at 1μM and10 μM, respectively both in hepatocytes and KCs. Dendrimer-induced Ca 2+ signals in hepatocytes were attenuated by macrophages. Activation of KCs by lipopolysaccharide and G5 decreased the inducibility of CYP2B1/2, which was restored by depleting the KCs with gadolinium-chloride and pentoxyphylline, suggesting a role of macrophages in the hindrance of CYP2B1/2 induction by G5 and lipopolysaccharide. In the H/KC, but not in the hepatocyte mono-culture, G5 reduced the canalicular efflux of bilirubin and stimulated the uptake and canalicular efflux of taurocholate. In conclusion, H/KC provides a good model for the prediction of hepatotoxic potential of drugs, especially of nanomaterials known to be trapped by macrophages, activation of which presumably contributes to DILI. Copyright © 2016 Elsevier B.V. All rights reserved.

  1. Radiation effects on biochemical systems

    International Nuclear Information System (INIS)

    Seddon, G.M.

    2000-04-01

    Xanthine oxidase catalyses the oxidative hydroxylation of hypoxanthine, xanthine and a wide range of carbonyl compounds. The enzyme exists as an oxidase and a dehydrogenase; both catalyze the oxidation of the same substrates. Steady state radiolysis and pulse radiolysis were used to generate oxidative and reductive free radicals. Their effects on the enzymatic activity of xanthine oxidase were determined. Initially inactivation studies were carried out to evaluate the extent to which radiolysis in aqueous solution affects the enzyme activity. Values of D 37 and G inactivation were calculated following irradiation in the presence of free radical scavengers and in the presence of catalase and superoxide dismutase. The kinetic constants Vmax and Km were also determined following radiolysis. The effect of ionising radiation on the iron content of xanthine oxidase was measured using atomic absorption spectrometry. Native gel electrophoresis and iso-electric focussing were performed in an attempt to demonstrate changes in the overall structure of the enzyme. The binding of xanthine oxidase to heparin was carried out by measuring, (1) the displacement of methylene blue (MB + ) from a heparin-MB + complex, (2) affinity chromatography and, (3) pulse radiolysis. The effect of irradiation on the binding process was investigated using techniques (1) and (2). Finally the radiation-induced conversion of xanthine oxidase to dehydrogenase was established. The results indicate that xanthine oxidase is inactivated greatest in the presence of air and irradiation causes Vmax to he reduced and Km to increase. The iron content of irradiated xanthine oxidase is unaffected. Electrophoresis shows the enzyme becomes fragmented and the isoelectric points of the fragments vary over a wide range of pH. Binding of xanthine oxidase to heparin as measured by displacement of MB + from a heparin-MB + complex suggests that irradiation increases the affinity of the enzyme for the polyanion, whereas

  2. Efficient encapsulation of antisense oligonucleotides in lipid vesicles using ionizable aminolipids: formation of novel small multilamellar vesicle structures.

    Science.gov (United States)

    Semple, S C; Klimuk, S K; Harasym, T O; Dos Santos, N; Ansell, S M; Wong, K F; Maurer, N; Stark, H; Cullis, P R; Hope, M J; Scherrer, P

    2001-02-09

    Typical methods used for encapsulating antisense oligodeoxynucleotides (ODN) and plasmid DNA in lipid vesicles result in very low encapsulation efficiencies or employ cationic lipids that exhibit unfavorable pharmacokinetic and toxicity characteristics when administered intravenously. In this study, we describe and characterize a novel formulation process that utilizes an ionizable aminolipid (1,2-dioleoyl-3-dimethylammonium propane, DODAP) and an ethanol-containing buffer system for encapsulating large quantities (0.15--0.25 g ODN/g lipid) of polyanionic ODN in lipid vesicles. This process requires the presence of up to 40% ethanol (v/v) and initial formulation at acidic pH values where the DODAP is positively charged. In addition, the presence of a poly(ethylene glycol)-lipid was required during the formulation process to prevent aggregation. The 'stabilized antisense-lipid particles' (SALP) formed are stable on adjustment of the external pH to neutral pH values and the formulation process allows encapsulation efficiencies of up to 70%. ODN encapsulation was confirmed by nuclease protection assays and (31)P NMR measurements. Cryo-electron microscopy indicated that the final particles consisted of a mixed population of unilamellar and small multilamellar vesicles (80--140 nm diameter), the relative proportion of which was dependent on the initial ODN to lipid ratio. Finally, SALP exhibited significantly enhanced circulation lifetimes in mice relative to free antisense ODN, cationic lipid/ODN complexes and SALP prepared with quaternary aminolipids. Given the small particle sizes and improved encapsulation efficiency, ODN to lipid ratios, and circulation times of this formulation compared to others, we believe SALP represent a viable candidate for systemic applications involving nucleic acid therapeutics.

  3. Physico-mechanical analysis data in support of compatibility of chitosan/κ-carrageenan polyelectrolyte films achieved by ascorbic acid, and the thermal degradation theory of κ-carrageenan influencing the properties of its blends

    Directory of Open Access Journals (Sweden)

    Mahdiyar Shahbazi

    2016-12-01

    Full Text Available This article presents the complementary data regarding compatibilization of chitosan/κ-carrageenan polyelectrolyte complex for synthesizing of a soft film using ascorbic acid. It includes the thermal-theory for estimating the degradation of κ-carrageenan, as reflected in alteration of the structural properties of the blend. The data has been provided to demonstrate that the blend solution based on chitosan, a polycation, and κ-carrageenan, a polyanion polymer, produces an incompatible polyelectrolyte composite, susceptible to coaservative phase separation. We present further data on water resistance, water barrier property, mechanical parameters, scanning electron micrograph, as well as contact angle image dataset of the chitosan/κ-carrageenan film. The physical data were collected by water solubility and water permeability assays, with a view to elucidate the role of ascorbic acid in the compatibility of polyelectrolyte blends. The mechanical data is obtained from a stress–strain curve for evaluation of tensile strength and elongation at break point of the chitosan/κ-carrageenan film. The microstructure observations were performed using scanning electron micrograph. These dataset confirm fabrication of a soft film in the presence of ascorbic acid, with reduced heterogeneities in the polyelectrolyte film structure. The κ-carrageenan was also treated by a thermal process, prior to inclusion into the chitosan solution, to investigate the impact of this on the mechanical and structural features of the resulting blend. We present the required data and the theoretical analysis supporting the thermal chain degradation of a polymer and its effects on behavior of the film. Additional information, characterizing the hydrophobicity of the surface of the blend layers is obtained by measuring water contact angles using a contact anglemeter.

  4. Surface-active biopolymers from marine bacteria for potential biotechnological applications

    Directory of Open Access Journals (Sweden)

    Karina Sałek

    2016-03-01

    Full Text Available Surface-active agents are amphiphilic chemicals that are used in almost every sector of modern industry, the bulk of which are produced by organo-chemical synthesis. Those produced from biological sources (biosurfactants and bioemulsifiers, however, have gained increasing interest in recent years due to their wide structural and functional diversity, lower toxicities and high biodegradability, compared to their chemically-synthesised counterparts. This review aims to present a general overview on surface-active agents, including their classification, where new types of these biomolecules may lay awaiting discovery, and some of the main bottlenecks for their industrial-scale production. In particular, the marine environment is highlighted as a largely untapped source for discovering new types of surface-active agents. Marine bacteria, especially those living associated with micro-algae (eukaryotic phytoplankton, are a highly promising source of polymeric surface-active agents with potential biotechnological applications. The high uronic acids content of these macromolecules has been linked to conferring them with amphiphilic qualities, and their high structural diversity and polyanionic nature endows them with the potential to exhibit a wide range of functional diversity. Production yields (e.g. by fermentation for most microbial surface-active agents have often been too low to meet the volume demands of industry, and this principally remains as the most important bottleneck for their further commercial development. However, new developments in recombinant and synthetic biology approaches can offer significant promise to alleviate this bottleneck. This review highlights a particular biotope in the marine environment that offers promise for discovering novel surface-active biomolecules, and gives a general overview on specific areas that researchers and the industry could focus work towards increasing the production yields of microbial surface

  5. Modification of nanoelectrode ensembles by thiols and disulfides to prevent non specific adsorption of proteins

    International Nuclear Information System (INIS)

    Silvestrini, M.; Schiavuta, P.; Scopece, P.; Pecchielan, G.; Moretto, L.M.; Ugo, P.

    2011-01-01

    Highlights: → Complex nanostructures are built on the gold surface of ensembles of nanoelectrodes. → Gold surface of nanoelectrodes was functionalized with SAM of organic sulphurs. → The polycarbonate surrounding nanoelectrodes was functionalized with proteins. → SAMs protect the nanoelectrodes from undesired proteins adsorption. - Abstract: The possibility to functionalize selectively with thiols or disulfides the surface of the gold nanoelectrodes of polycarbonate templated nanoelectrode ensembles (NEEs) is studied. It is shown that the Au nanoelectrodes can be coated by a self assembled monolayer (SAM) of thioctic acid (TA) or 2-mercaptoethanesulfonic (MES) acid. The study of the electrochemical behavior of SAM-modified NEEs by cyclic voltammetry (CV) at different solution pH, using ferrocenecarboxylate as an anionic redox probe (FcCOO - ) and (ferrocenylmethyl)trimethylammonium (FA + ) as a cationic redox probe, demonstrate that the SAM-modified nanoelectrodes are permselective, in that only cationic or neutral probes can access the SAM-coated nanoelectrode surface. CV, AFM and FTIR-ATR data indicate that proteins such as casein or bovine serum albumin, which are polyanionic at pH 7, adsorb on the surface of NEEs untreated with thiols, tending to block the electron transfer of the ferrocenyl redox probes. On the contrary, the pre-treatment of the NEE with an anionic SAM protects the nanoelectrodes from protein fouling, allowing the detection of well shaped voltammetric patterns for the redox probe. Experimental results indicate that, in the case of MES treated NEEs, the protein is bound only onto the polycarbonate surface which surrounds the nanoelectrodes, while the tips of the gold nanoelectrodes remain protein free.

  6. Cation–Anion Interactions within the Nucleic Acid Ion Atmosphere Revealed by Ion Counting

    Science.gov (United States)

    Gebala, Magdalena; Giambasu, George M.; Lipfert, Jan; Bisaria, Namita; Bonilla, Steve; Li, Guangchao; York, Darrin M.; Herschlag, Daniel

    2016-01-01

    The ion atmosphere is a critical structural, dynamic, and energetic component of nucleic acids that profoundly affects their interactions with proteins and ligands. Experimental methods that “count” the number of ions thermodynamically associated with the ion atmosphere allow dissection of energetic properties of the ion atmosphere, and thus provide direct comparison to theoretical results. Previous experiments have focused primarily on the cations that are attracted to nucleic acid polyanions, but have also showed that anions are excluded from the ion atmosphere. Herein, we have systematically explored the properties of anion exclusion, testing the zeroth-order model that anions of different identity are equally excluded due to electrostatic repulsion. Using a series of monovalent salts, we find, surprisingly, that the extent of anion exclusion and cation inclusion significantly depends on salt identity. The differences are prominent at higher concentrations and mirror trends in mean activity coefficients of the electrolyte solutions. Salts with lower activity coefficients exhibit greater accumulation of both cations and anions within the ion atmosphere, strongly suggesting that cation–anion correlation effects are present in the ion atmosphere and need to be accounted for to understand electrostatic interactions of nucleic acids. To test whether the effects of cation–anion correlations extend to nucleic acid kinetics and thermodynamics, we followed the folding of P4–P6, a domain of the Tetrahymena group I ribozyme, via single-molecule fluorescence resonance energy transfer in solutions with different salts. Solutions of identical concentration but lower activity gave slower and less favorable folding. Our results reveal hitherto unknown properties of the ion atmosphere and suggest possible roles of oriented ion pairs or anion-bridged cations in the ion atmosphere for electrolyte solutions of salts with reduced activity. Consideration of these new

  7. Surface analysis monitoring of polyelectrolyte deposition on Ba0.5Sr0.5TiO3 thin films

    International Nuclear Information System (INIS)

    Morales-Cruz, Angel L.; Fachini, Estevao R.; Miranda, Felix A.; Cabrera, Carlos R.

    2007-01-01

    Thin films are currently gaining interest in many areas such as integrated optics, sensors, friction, reducing coatings, surface orientation layers, and general industrial applications. Recently, molecular self-assembling techniques have been applied for thin film deposition of electrically conducting polymers, conjugated polymers for light-emitting devices, nanoparticles, and noncentrosymmetric-ordered second order nonlinear optical (NOL) devices. Polyelectrolytes self-assemblies have been used to prepare thin films. The alternate immersion of a charged surface in polyannion and a polycation solution leads usually to the formation of films known as polyelectrolyte multilayers. These polyanion and polycation structures are not neutral. However, charge compensation appears on the surface. This constitutes the building driving force of the polyelectrolyte multilayer films. The present approach consists of two parts: (a) the chemisorption of 11-mercaptoundecylamine (MUA) to construct a self-assembled monolayer with the consequent protonation of the amine, and (b) the deposition of opposite charged polyelectrolytes in a sandwich fashion. The approach has the advantage that ionic attraction between opposite charges is the driving force for the multilayer buildup. For our purposes, the multilayer of polyelectrolytes depends on the quality of the surface needed for the application. In many cases, this approach will be used in a way that the roughness factor defects will be diminished. The polyelectrolytes selected for the study were: polystyrene sulfonate sodium salt (PSS), poly vinylsulfate potassium salt (PVS), and polyallylamine hydrochloride (PAH), as shown in . The deposition of polyelectrolytes was carried out by a dipping procedure with the corresponding polyelectrolyte. Monitoring of the alternate deposition of polyelectrolyte bilayers was done by surface analysis techniques such as X-ray photoelectron spectroscopy (XPS), specular reflectance infrared (IR), and

  8. Charge neutralization as the major factor for the assembly of nucleocapsid-like particles from C-terminal truncated hepatitis C virus core protein

    Directory of Open Access Journals (Sweden)

    Theo Luiz Ferraz de Souza

    2016-11-01

    Full Text Available Background Hepatitis C virus (HCV core protein, in addition to its structural role to form the nucleocapsid assembly, plays a critical role in HCV pathogenesis by interfering in several cellular processes, including microRNA and mRNA homeostasis. The C-terminal truncated HCV core protein (C124 is intrinsically unstructured in solution and is able to interact with unspecific nucleic acids, in the micromolar range, and to assemble into nucleocapsid-like particles (NLPs in vitro. The specificity and propensity of C124 to the assembly and its implications on HCV pathogenesis are not well understood. Methods Spectroscopic techniques, transmission electron microscopy and calorimetry were used to better understand the propensity of C124 to fold or to multimerize into NLPs when subjected to different conditions or in the presence of unspecific nucleic acids of equivalent size to cellular microRNAs. Results The structural analysis indicated that C124 has low propensity to self-folding. On the other hand, for the first time, we show that C124, in the absence of nucleic acids, multimerizes into empty NLPs when subjected to a pH close to its isoelectric point (pH ≈ 12, indicating that assembly is mainly driven by charge neutralization. Isothermal calorimetry data showed that the assembly of NLPs promoted by nucleic acids is enthalpy driven. Additionally, data obtained from fluorescence correlation spectroscopy show that C124, in nanomolar range, was able to interact and to sequester a large number of short unspecific nucleic acids into NLPs. Discussion Together, our data showed that the charge neutralization is the major factor for the nucleocapsid-like particles assembly from C-terminal truncated HCV core protein. This finding suggests that HCV core protein may physically interact with unspecific cellular polyanions, which may correspond to microRNAs and mRNAs in a host cell infected by HCV, triggering their confinement into infectious particles.

  9. ThSi_2 type ytterbium disilicide and its analogues YbT_xSi_2_-_x (T = Cr, Fe, Co)

    International Nuclear Information System (INIS)

    Peter, Sebastian C.; Kanatzidis, Mercouri G.

    2012-01-01

    YbSi_2 and the derivatives YbT_xSi_2_-_x (T = Cr, Fe, Co) crystallizing in the α-ThSi_2 structure type were obtained as single crystals from reactions run in liquid indium. All silicides were investigated by single-crystal X-ray diffraction, I4_1/amd space group and the lattice constants are: a = 3.9868(6) Aa and c = 13.541(3) Aa for YbSi_2, a = 4.0123(6) Aa and c = 13.542(3) Aa for YbCr_0_._2_7Si_1_._7_3, a = 4.0142(6) Aa and c = 13.830(3) Aa for YbCr_0_._7_1Si_1_._2_9, a = 4.0080(6) Aa and c = 13.751(3) Aa for YbFe_0_._3_4Si_1_._6_6, and a = 4.0036(6) Aa, c = 13.707(3) Aa for YbCo_0_._2_1Si_1_._7_9. YbSi_2 and YbT_xSi_2_-_x compounds are polar intermetallics with three-dimensional Si and M (T+Si) polyanion sub-networks, respectively, filled with ytterbium atoms. The degree of substitution of transition metal at the silicon site is signficant and leads to changes in the average bond lengths and bond angles substantially. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  10. Polycation induced actin bundles.

    Science.gov (United States)

    Muhlrad, Andras; Grintsevich, Elena E; Reisler, Emil

    2011-04-01

    Three polycations, polylysine, the polyamine spermine and the polycationic protein lysozyme were used to study the formation, structure, ionic strength sensitivity and dissociation of polycation-induced actin bundles. Bundles form fast, simultaneously with the polymerization of MgATP-G-actins, upon the addition of polycations to solutions of actins at low ionic strength conditions. This indicates that nuclei and/or nascent filaments bundle due to attractive, electrostatic effect of polycations and the neutralization of repulsive interactions of negative charges on actin. The attractive forces between the filaments are strong, as shown by the low (in nanomolar range) critical concentration of their bundling at low ionic strength. These bundles are sensitive to ionic strength and disassemble partially in 100 mM NaCl, but both the dissociation and ionic strength sensitivity can be countered by higher polycation concentrations. Cys374 residues of actin monomers residing on neighboring filaments in the bundles can be cross-linked by the short span (5.4Å) MTS-1 (1,1-methanedyl bismethanethiosulfonate) cross-linker, which indicates a tight packing of filaments in the bundles. The interfilament cross-links, which connect monomers located on oppositely oriented filaments, prevent disassembly of bundles at high ionic strength. Cofilin and the polysaccharide polyanion heparin disassemble lysozyme induced actin bundles more effectively than the polylysine-induced bundles. The actin-lysozyme bundles are pathologically significant as both proteins are found in the pulmonary airways of cystic fibrosis patients. Their bundles contribute to the formation of viscous mucus, which is the main cause of breathing difficulties and eventual death in this disorder. Copyright © 2011 Elsevier B.V. All rights reserved.

  11. The role of the class A scavenger receptors, SR-A and MARCO, in the immune system. Part 1. The structure of receptors, their ligand binding repertoires and ability to initiate intracellular signaling

    Directory of Open Access Journals (Sweden)

    Szczepan Józefowski

    2012-02-01

    Full Text Available  Recognition of pathogens by innate immune cells is mediated by pattern recognition receptors (PRR, which include scavenger receptors (SR. The class A SR, SR-A/CD204 and MARCO, are characterized by the presence of collagenous and SR cysteine-rich domains in their extracellular portions. Both receptors are expressed mainly on macrophages and dendritic cells. Thanks to their ability to bind to a wide range of polyanionic ligands, the class A SR may participate in numerous functions of these cells, such as endocytosis, and adhesion to extracellular matrix and to other cells. Among SR-A ligands are oxidized lipoproteins and β-amyloid fibrils, which link SR-A to the pathogenesis of arteriosclerosis and Alzheimer’s disease. Despite the demonstration of class A SR involvement in so many processes, the lack of selective ligands precluded reaching definite conclusions concerning their signaling abilities. Using specific receptor ligation with antibodies, we showed that SR-A and MARCO trigger intracellular signaling, modulating pro-inflammatory and microbicidal activities of macrophages. Surprisingly, despite similarities in structure and ligand binding repertoires, SR-A and MARCO exert opposite effects on interleukin-12 (IL-12 production in macrophages. SR-A ligation also stimulated H2O2 and IL-10 production, but had no effect on the release of several other cytokines. These limited effects of specific SR-A ligation contrast with generalized enhancement of immune responses observed in SR-A-deficient mice. Recent studies have revealed that many of these effects of SR-A deficiency may be caused by compensatory changes in the expression of other receptors and/or disinhibition of signal transduction from receptors belonging to the Toll/IL-1R family, rather than by the loss of the receptor function of SR-A.

  12. Superstructure formation in PrNi{sub 2}Al{sub 3} and ErPd{sub 2}Al{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Eustermann, Fabian; Hoffmann, Rolf-Dieter [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie; Janka, Oliver [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie; Oldenburg Univ. (Germany). Inst. fuer Chemie

    2017-09-01

    The intermetallic phase ErPd{sub 2}Al{sub 3} was obtained by arc-melting of the elements and subsequent annealing for crystal growth. The sample was studied by X-ray diffraction on powders and single crystals. The structure of ErPd{sub 2}Al{sub 3} was refined from X-ray diffraction data and revealed a superstructure of PrNi{sub 2}Al{sub 3} - a CaCu{sub 5} derivative (P6/m, a=1414.3(1), c=418.87(3) pm wR=0.0820, 1060 F{sup 2} values, 48 variables). The same superstructure was subsequently found for PrNi{sub 2}Al{sub 3} (P6/m, a=1407.87(4), c=406.19(2) pm, wR=0.0499, 904 F{sup 2} values, 47 variables). In the crystal structure, the aluminium and transition metal atoms form a polyanionic network according to [T{sub 2}Al{sub 3}]{sup δ-}, while rare earth atoms fill cavities within the networks. They are coordinated by six transition metal and twelve aluminum atoms. In contrast to the PrNi{sub 2}Al{sub 3} type structure reported so far, two crystallographic independent rare-earth sites are found of which one (1b) is shifted by 1/2 z, causing a distortion in the structure along with a recoloring of the T and Al atoms in the network.

  13. Rhodium-rich silicides RERh{sub 6}Si{sub 4} (RE=La, Nd, Tb, Dy, Er, Yb)

    Energy Technology Data Exchange (ETDEWEB)

    Vosswinkel, Daniel; Poettgen, Rainer [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie

    2017-07-01

    Polycrystalline RERh{sub 6}Si{sub 4} (RE=La, Nd, Tb, Dy, Er, Yb) samples can be synthesized by arc-melting of the elements. Single crystals of LaRh{sub 6}Si{sub 4}, NdRh{sub 6}Si{sub 4} and YbRh{sub 6}Si{sub 4} were synthesized from the elements in bismuth fluxes (non-reactive flux medium). The structures were refined on the basis of single-crystal X-ray diffractometer data: LiCo{sub 6}P{sub 4} type, P anti 6m2, a=700.56(3), c=380.55(1) pm, wR2=0.0257, 317 F{sup 2} values, 19 variables for LaRh{sub 6}Si{sub 4}, a=698.4(5), c=377.7(2) pm, wR2=0.0578, 219 F{sup 2} values, 19 variables for NdRh{sub 6}Si{sub 4} and a=696.00(3), c=371.97(1) pm, wR2=0.0440, 309 F{sup 2} values, 19 variables for YbRh{sub 6}Si{sub 4}. The rhodium and silicon atoms build up three-dimensional, covalently bonded [Rh{sub 6}Si{sub 4}]{sup δ-} polyanionic networks with Rh-Si distances ranging from 239 to 249 pm. The rare earth atoms fill larger cavities within channels of these networks and they are coordinated by six silicon and twelve rhodium atoms in the form of hexa-capped hexagonal prisms.

  14. Ternary germanides RERhGe{sub 2} (RE = Y, Gd-Ho) – New representatives of the YIrGe{sub 2} type

    Energy Technology Data Exchange (ETDEWEB)

    Voßwinkel, Daniel; Heletta, Lukas; Hoffmann, Rolf-Dieter; Pöttgen, Rainer, E-mail: pottgen@uni-muenster.de

    2016-11-15

    The YIrGe{sub 2} type ternary germanides RERhGe{sub 2} (RE = Y, Gd-Ho) were synthesized from the elements by arc-melting and characterized by powder X-ray diffraction. The structure of DyRhGe{sub 2} was refined from single crystal X-ray diffractometer data: Immm, a = 426.49(9), b = 885.0(2), c = 1577.4(3) pm, wR2 = 0.0533, 637 F{sup 2} values, 30 variables (300 K data). The structure contains two crystallographically independent dysprosium atoms in pentagonal prismatic and hexagonal prismatic coordination. The three-dimensional [RhGe{sub 2}] polyanion is stabilized through covalent Rh–Ge (243–261 pm) and Ge–Ge (245–251 pm) bonding. The close structural relationship with the slightly rhodium-poorer germanides RE{sub 5}Rh{sub 4}Ge{sub 10} (≡ RERh{sub 0.8}Ge{sub 2}) is discussed. Temperature-dependent magnetic susceptibility measurements reveal Pauli paramagnetism for YRhGe{sub 2} and Curie-Weiss paramagnetism for RERhGe{sub 2} with RE = Gd, Tb, Dy and Ho. These germanides order antiferromagnetically at T{sub N} = 7.2(5), 10.6(5), 8.1(5), and 6.4(5) K, respectively. - Graphical abstract: The germanides RERhGe{sub 2} (RE = Y, Gd-Ho) are new representatives of the YIrGe{sub 2} type.

  15. Lignosulfonic acid exhibits broadly anti-HIV-1 activity--potential as a microbicide candidate for the prevention of HIV-1 sexual transmission.

    Directory of Open Access Journals (Sweden)

    Min Qiu

    Full Text Available Some secondary metabolites from plants show to have potent inhibitory activities against microbial pathogens, such as human immunodeficiency virus (HIV, herpes simplex virus (HSV, Treponema pallidum, Neisseria gonorrhoeae, etc. Here we report that lignosulfonic acid (LSA, a polymeric lignin derivative, exhibits potent and broad activity against HIV-1 isolates of diverse subtypes including two North America strains and a number of Chinese clinical isolates values ranging from 21.4 to 633 nM. Distinct from other polyanions, LSA functions as an entry inhibitor with multiple targets on viral gp120 as well as on host receptor CD4 and co-receptors CCR5/CXCR4. LSA blocks viral entry as determined by time-of-drug addiction and cell-cell fusion assays. Moreover, LSA inhibits CD4-gp120 interaction by blocking the binding of antibodies specific for CD4-binding sites (CD4bs and for the V3 loop of gp120. Similarly, LSA interacts with CCR5 and CXCR4 via its inhibition of specific anti-CCR5 and anti-CXCR4 antibodies, respectively. Interestingly, the combination of LSA with AZT and Nevirapine exhibits synergism in viral inhibition. For the purpose of microbicide development, LSA displays low in vitro cytotoxicity to human genital tract epithelial cells, does not stimulate NF-κB activation and has no significant up-regulation of IL-1α/β and IL-8 as compared with N-9. Lastly, LSA shows no adverse effect on the epithelial integrity and the junctional protein expression. Taken together, our findings suggest that LSA can be a potential candidate for tropical microbicide.

  16. Emulsion-core and polyelectrolyte-shell nanocapsules: biocompatibility and neuroprotection against SH-SY5Y cells

    Energy Technology Data Exchange (ETDEWEB)

    Piotrowski, Marek, E-mail: ncpiotro@cyf-kr.edu.pl; Szczepanowicz, Krzysztof [Polish Academy of Sciences, Jerzy Haber Institute of Catalysis and Surface Chemistry (Poland); Jantas, Danuta; Leśkiewicz, Monika; Lasoń, Władysław [Polish Academy of Sciences, Institute of Pharmacology (Poland); Warszyński, Piotr [Polish Academy of Sciences, Jerzy Haber Institute of Catalysis and Surface Chemistry (Poland)

    2013-11-15

    The emulsion-core and polyelectrolyte-coated nanocapsules, designed as water-insoluble neuroprotective drug delivery system, were synthesized using layer-by-layer saturation method. The isopropyl myristate was used as oil phase and docusate sodium salt as emulsifier. For the polyelectrolyte shell preparation, synthetic polyelectrolytes, cationic (PDADMAC, PAH, and PLL) and anionic (PGA) were used. The particle size and zeta potential of nanocapsules were characterized by the dynamic light scattering. The average size of synthesized nanocapsules ranged from ∼80 to ∼100 nm. Zeta potential values ranged from less than approximately −30 mV for the polyanion layers to greater than approximately +30 mV for the polycation layers. Biocompatibilities of the synthesized nanocarriers were evaluated against SH-SY5Y human neuroblastoma cells using various biochemical assays. The results obtained show that synthesized nanocapsules coated with PLL and PGA were nontoxic to SH-SY5Y cells, and they were used as nanocarriers for model neuroprotective drug (a calpain inhibitor MDL 28170). The neuroprotective action of the encapsulated MDL 28170 against hydrogen peroxide-induced oxidative stress cytotoxicity was evaluated in the same cell line. The results showed that nanoencapsulated form of MDL 28170 were biocompatible and protected SH-SY5Y cells against the H{sub 2}O{sub 2} (0.5 mM/24 h)-induced damage in 20–40 times lower concentrations than those of the same drug added directly to the culture medium. These data suggest that the nanoscale carriers of neuroprotective drugs might serve as novel promising therapeutic agents for oxidative stress-related neurodegenerative processes.

  17. One-electron oxidation of DNA: mechanism and consequences.

    Science.gov (United States)

    Schuster, Gary B

    2009-01-01

    All living organisms store the information necessary to maintain life in their DNA. Any process that damages DNA and causes loss or corruption of that information threatens the viability of the organism. One-electron oxidation is such a process. Loss of an electron from DNA generates a radical cation that is located primarily on its nucleobases. The radical cation migrates reversibly through duplex DNA by hopping until it is eventually trapped in an irreversible chemical reaction. The particular sequence of nucleobases in a DNA oligomer determines both the efficiency of hopping and the specific location and nature of the damaging chemical reaction. In its normal aqueous solutions, DNA is a polyanion because of the negative charge carried by its phosphate groups. Counter ions (typically Na(+)) to the phosphate groups play an important role in facilitating both the migration of the radical cation and in its eventual reaction with H(2)O. Irreversible reaction of a radical cation with H(2)O in duplex DNA occurs preferentially at the most reactive site. In normal DNA that is comprised of the four common DNA nucleobases, reaction occurs most commonly at a guanine and results in its conversion primarily to 8-oxo-7,8-dihydroguanine (8-OxoG). Both electronic and steric effects control the outcome of this process. If the DNA oligomer does not contain a suitable guanine, then reaction of the radical cation occurs at the thymine of a TT step primarily by a tandem process. The general outcomes revealed in the one-electron oxidation of DNA oligomers in solution appear to be generally valid also for more complex DNA structures and for the cellular DNA of living organisms.

  18. Pretreatment-dependent surface chemistry of wood nanocellulose for pH-sensitive hydrogels.

    Science.gov (United States)

    Chinga-Carrasco, Gary; Syverud, Kristin

    2014-09-01

    Nanocellulose from wood is a promising material with potential in various technological areas. Within biomedical applications, nanocellulose has been proposed as a suitable nano-material for wound dressings. This is based on the capability of the material to self-assemble into 3D micro-porous structures, which among others have an excellent capacity of maintaining a moist environment. In addition, the surface chemistry of nanocellulose is suitable for various applications. First, OH-groups are abundant in nanocellulose materials, making the material strongly hydrophilic. Second, the surface chemistry can be modified, introducing aldehyde and carboxyl groups, which have major potential for surface functionalization. In this study, we demonstrate the production of nanocellulose with tailor-made surface chemistry, by pre-treating the raw cellulose fibres with carboxymethylation and periodate oxidation. The pre-treatments yielded a highly nanofibrillated material, with significant amounts of aldehyde and carboxyl groups. Importantly, the poly-anionic surface of the oxidized nanocellulose opens up for novel applications, i.e. micro-porous materials with pH-responsive characteristics. This is due to the swelling capacity of the 3D micro-porous structures, which have ionisable functional groups. In this study, we demonstrated that nanocellulose gels have a significantly higher swelling degree in neutral and alkaline conditions, compared to an acid environment (pH 3). Such a capability can potentially be applied in chronic wounds for controlled and intelligent release of antibacterial components into biofilms. © The Author(s) 2014 Reprints and permissions: sagepub.co.uk/journalsPermissions.nav.

  19. Chitosan microspheres in novel drug delivery systems.

    Science.gov (United States)

    Mitra, Analava; Dey, Baishakhi

    2011-07-01

    The main aim in the drug therapy of any disease is to attain the desired therapeutic concentration of the drug in plasma or at the site of action and maintain it for the entire duration of treatment. A drug on being used in conventional dosage forms leads to unavoidable fluctuations in the drug concentration leading to under medication or overmedication and increased frequency of dose administration as well as poor patient compliance. To minimize drug degradation and loss, to prevent harmful side effects and to increase drug bioavailability various drug delivery and drug targeting systems are currently under development. Handling the treatment of severe disease conditions has necessitated the development of innovative ideas to modify drug delivery techniques. Drug targeting means delivery of the drug-loaded system to the site of interest. Drug carrier systems include polymers, micelles, microcapsules, liposomes and lipoproteins to name some. Different polymer carriers exert different effects on drug delivery. Synthetic polymers are usually non-biocompatible, non-biodegradable and expensive. Natural polymers such as chitin and chitosan are devoid of such problems. Chitosan comes from the deacetylation of chitin, a natural biopolymer originating from crustacean shells. Chitosan is a biocompatible, biodegradable, and nontoxic natural polymer with excellent film-forming ability. Being of cationic character, chitosan is able to react with polyanions giving rise to polyelectrolyte complexes. Hence chitosan has become a promising natural polymer for the preparation of microspheres/nanospheres and microcapsules. The techniques employed to microencapsulate with chitosan include ionotropic gelation, spray drying, emulsion phase separation, simple and complex coacervation. This review focuses on the preparation, characterization of chitosan microspheres and their role in novel drug delivery systems.

  20. N-[3H]acetyl-labeling, a convenient method for radiolabeling of glycosaminoglycans

    International Nuclear Information System (INIS)

    Hook, M.; Riesenfeld, J.; Lindahl, U.

    1982-01-01

    A method for the introduction of N-[ 3 H]acetyl groups into glycosaminoglycans is described. The procedure is based on [ 3 H]acetylation of N-unsubstituted hexosamine residues by treating the polysaccharides with [ 3 H]acetic anhydride. Preparations of heparin and heparin sulfate were found to contain significant numbers of N-unsubstituted hexosamine residues, as isolates. In contrast, such units could not be detected in chondroitin sulfate, dermatan sulfate, or hyaluronic acid. These polysaccharides were therefore subjected to partial N-deacetylation by reaction with hydrazine in the presence of hydrazine sulfate. After treatment with [ 3 H]acetic anhydride, the specific activities of the resulting labeled polysaccharide preparations ranged between 0.1 X 10 6 and 0.6 X 10 6 cpm 3 H/μg of uronic acid. The 3 H-labeled polysaccharide preparations did not differ significantly from the corresponding unlabeled starting materials with regard to polyanion properties (chromatography on DEAE-cellulose) or polymer chain size (gel chromatography). Further, the radiolabeled polysaccharide derivatives were susceptible to specific enzymatic degradation (chondroitinase ABC and mammalian heparitinase) and retained their ability to interact specifically with certain proteins - for example, [ 3 H]heparin with antithrombin [ 3 H]hyaluronic acid oligosaccharides with chondroitin sulfate proteoglycan. These findings indicate that the labeling procedures did not induce any major structural derangement of the polysaccharide molecules. The method developed should be useful in providing labeled glycosaminoglycans for metabolic and enzymatic experiments as well as for studies on the interacion between glycosaminoglycans and other bilogical macromolecules

  1. Un-repairable DNA damage in cell due to irradiation

    International Nuclear Information System (INIS)

    Yoshii, Giichi

    1992-01-01

    Radiation-induced cell reproductive deactivation is caused by damage to DNA. In a cell, cellular DNA radical reacts with diffusion controlled rate and generates DNA peroxide radical. The chemical repair of DNA radical with hydrogen donation by thiol competes with the reaction of oxygen with same radicals in the DNA molecules. From the point reaction rates, the prolongation of radical life time is not as great as expected from the reduction in the glutathione content of the cell. This indicates that further reducting compounds (protein bound thiol) are present in the cell. The residual radicals are altered to strand breaks, base damages and so on. The effective lesions for a number of endpoints is un-repaired double strand break, which has been discovered in a cluster. This event gives risk to high LET radiation or to a track end of X-rays. For X- or electron irradiations the strand breaks are frequently induced by the interactions between sublesions on two strands in DNA. A single strand break followed by radical action may be unstable excited state, because of remaining sugar radical action and of having negative charged phosphates, in which strands breaks will be rejoined in a short time to stable state. On the same time, a break in the double helix will be immediately produced if two breaks are on either or approximately opposite locations. The formation of a double strand break in the helix depends on the ion strength of the cell. The potassium ions are largely released from polyanionic strand during irradiation, which results in the induction of denatured region. Double strand break with the denatured region seems to be un-repairable DNA damage. (author)

  2. Effects of citrate on hexavalent chromium reduction by structural Fe(II) in nontronite

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Xiaolei; Dong, Hailiang; Yang, Xuewei; Kovarik, Libor; Chen, Yu; Zeng, Qiang

    2018-02-01

    Iron-bearing clay minerals and organic matter are two important components in natural environments that influence hexavalent chromium (Cr(VI)) reduction. Previous studies have shown that organic ligands could influence Cr(VI) reduction by aqueous Fe2+ and pyrite. However, the effects of organic ligands on Cr(VI) reduction by structural Fe(II) in clays are not well understood. In this study, the effects of citrate on Cr(VI) reduction by nontronite (NAu-2) were investigated under near neutral pH condition (pH=6). Our results showed that the presence of citrate decreased the rate but increased the amount of Cr(VI) reduction by structural Fe(II) in NAu-2. The decreased reaction rate was likely due to competitive sorption of citrate and polyanionic dichromate (Cr2O7- ), because sorption of dichromate appeared to be the first step for subsequent Cr(VI) reduction. The increased amount of Cr(VI) reduction in the presence of citrate was likely because citrate provided additional reducing power through ligand-metal electron transfer in the presence of soluble Fe 3+ derived from dissolution of reduced NAu-2. Soluble Cr(III)-citrate complex was the possible form of reduced chromium when citrate was present. In contrast, nanometer-sized Cr2O3 particles were the product of Cr(VI) reduction by reduced NAu-2 without citrate. Our study highlights the importance of organic ligands on Cr(VI) reduction and immobilization when iron-bearing clay minerals are applied to treat Cr(VI) contaminant in organic matter rich environments.

  3. Ternary polyplex micelles with PEG shells and intermediate barrier to complexed DNA cores for efficient systemic gene delivery.

    Science.gov (United States)

    Li, Junjie; Chen, Qixian; Zha, Zengshi; Li, Hui; Toh, Kazuko; Dirisala, Anjaneyulu; Matsumoto, Yu; Osada, Kensuke; Kataoka, Kazunori; Ge, Zhishen

    2015-07-10

    Simultaneous achievement of prolonged retention in blood circulation and efficient gene transfection activity in target tissues has always been a major challenge hindering in vivo applications of nonviral gene vectors via systemic administration. Herein, we constructed novel rod-shaped ternary polyplex micelles (TPMs) via complexation between the mixed block copolymers of poly(ethylene glycol)-b-poly{N'-[N-(2-aminoethyl)-2-aminoethyl]aspartamide} (PEG-b-PAsp(DET)) and poly(N-isopropylacrylamide)-b-PAsp(DET) (PNIPAM-b-PAsp(DET)) and plasmid DNA (pDNA) at room temperature, exhibiting distinct temperature-responsive formation of a hydrophobic intermediate layer between PEG shells and pDNA cores through facile temperature increase from room temperature to body temperature (~37 °C). As compared with binary polyplex micelles of PEG-b-PAsp(DET) (BPMs), TPMs were confirmed to condense pDNA into a more compact structure, which achieved enhanced tolerability to nuclease digestion and strong counter polyanion exchange. In vitro gene transfection results demonstrated TPMs exhibiting enhanced gene transfection efficiency due to efficient cellular uptake and endosomal escape. Moreover, in vivo performance evaluation after intravenous injection confirmed that TPMs achieved significantly prolonged blood circulation, high tumor accumulation, and promoted gene expression in tumor tissue. Moreover, TPMs loading therapeutic pDNA encoding an anti-angiogenic protein remarkably suppressed tumor growth following intravenous injection into H22 tumor-bearing mice. These results suggest TPMs with PEG shells and facilely engineered intermediate barrier to inner complexed pDNA have great potentials as systemic nonviral gene vectors for cancer gene therapy. Copyright © 2015 Elsevier B.V. All rights reserved.

  4. Arc is a flexible modular protein capable of reversible self-oligomerization

    Science.gov (United States)

    Myrum, Craig; Baumann, Anne; Bustad, Helene J.; Flydal, Marte Innselset; Mariaule, Vincent; Alvira, Sara; Cuéllar, Jorge; Haavik, Jan; Soulé, Jonathan; Valpuesta, José Maria; Márquez, José Antonio; Martinez, Aurora; Bramham, Clive R.

    2015-01-01

    The immediate early gene product Arc (activity-regulated cytoskeleton-associated protein) is posited as a master regulator of long-term synaptic plasticity and memory. However, the physicochemical and structural properties of Arc have not been elucidated. In the present study, we expressed and purified recombinant human Arc (hArc) and performed the first biochemical and biophysical analysis of hArc's structure and stability. Limited proteolysis assays and MS analysis indicate that hArc has two major domains on either side of a central more disordered linker region, consistent with in silico structure predictions. hArc's secondary structure was estimated using CD, and stability was analysed by CD-monitored thermal denaturation and differential scanning fluorimetry (DSF). Oligomerization states under different conditions were studied by dynamic light scattering (DLS) and visualized by AFM and EM. Biophysical analyses show that hArc is a modular protein with defined secondary structure and loose tertiary structure. hArc appears to be pyramid-shaped as a monomer and is capable of reversible self-association, forming large soluble oligomers. The N-terminal domain of hArc is highly basic, which may promote interaction with cytoskeletal structures or other polyanionic surfaces, whereas the C-terminal domain is acidic and stabilized by ionic conditions that promote oligomerization. Upon binding of presenilin-1 (PS1) peptide, hArc undergoes a large structural change. A non-synonymous genetic variant of hArc (V231G) showed properties similar to the wild-type (WT) protein. We conclude that hArc is a flexible multi-domain protein that exists in monomeric and oligomeric forms, compatible with a diverse, hub-like role in plasticity-related processes. PMID:25748042

  5. The collagen type I segment long spacing (SLS) and fibrillar forms: Formation by ATP and sulphonated diazo dyes.

    Science.gov (United States)

    Harris, J Robin; Lewis, Richard J

    2016-07-01

    The collagen type I segment long spacing (SLS) crystallite is a well-ordered rod-like molecular aggregate, ∼300nm in length, which is produced in vitro under mildly acidic conditions (pH 2.5-3.5) in the presence of 1mM ATP. The formation of the SLS crystallite amplifies the inherent linear structural features of individual collagen heterotrimers, due to the punctate linear distribution and summation of the bulkier amino acid side chains along the length of individual collagen heterotrimers. This can be correlated structurally with the 67nm D-banded collagen fibril that is found in vivo, and formed in vitro. Although first described many years ago, the range of conditions required for ATP-induced SLS crystallite formation from acid-soluble collagen have not been explored extensively. Consequently, we have addressed biochemical parameters such as the ATP concentration, pH, speed of formation and stability so as to provide a more complete structural understanding of the SLS crystallite. Treatment of collagen type I with 1mM ATP at neutral and higher pH (6.0-9.0) also induced the formation of D-banded fibrils. Contrary to previous studies, we have shown that the polysulphonated diazo dyes Direct red (Sirius red) and Evans blue, but not Congo red and Methyl blue, can also induce the formation of SLS-like aggregates of collagen, but under markedly different ionic conditions to those employed in the presence of ATP. Specifically, pre-formed D-banded collagen fibrils, prepared in a higher than the usual physiological NaCl concentration (e.g. 500mM NaCl, 20mM Tris-HCl pH7.4 or x3 PBS), readily form SLS aggregates when treated with 0.1mM Direct red and Evans blue, but this did not occur at lower NaCl concentrations. These new data are discussed in relation to the anion (Cl(-)) and polyanion (phosphate and sulphonate) binding by the collagen heterotrimer and their likely role in collagen fibrillogenesis and SLS formation. Copyright © 2016 Elsevier Ltd. All rights reserved.

  6. Polyelectrolyte Properties in Mono and Multi-Valent Ionic Media: Brushes and Complex Coacervates

    Science.gov (United States)

    Farina, Robert M.

    Materials composed of polyelectrolytes have unique and interesting physical properties resulting primarily from their charged monomer segments. Polyelectrolytes, which exist in many different biological and industrial forms, have also been shown to be highly responsive to external environmental changes. Here, two specific polyelectrolyte systems, brushes and complex coacervates, are discussed in regards to how their properties can be tailored by adjusting the surrounding ionic environment with mono and multi-valent ions. End-tethered polyelectrolyte brushes, which constitute an interesting and substantial portion of polyelectrolyte applications, are well known for their ability to provide excellent lubrication and low friction when coated onto surfaces (e.g. articular cartilage and medical devices), as well as for their ability to stabilize colloidal particles in solution (e.g. paint and cosmetic materials). These properties have been extensively studied with brushes in pure mono-valent ionic media. However, polyelectrolyte brush interactions with multi-valent ions in solution are much less understood, although highly relevant considering mono and multi-valent counterions are present in most applications. Even at very low concentrations of multi-valent ions in solution, dramatic polyelectrolyte brush physical property changes can occur, resulting in collapsed chains which also adhere to one another via multi-valent bridging. Here, the strong polyelectrolyte poly(sodium styrene sulfonate) was studied using the Surface Forces Apparatus (SFA) and electrochemistry in order to investigate brush height and intermolecular interactions between two brushes as a function of multi-valent counterion population inside a brush. Complex coacervates are formed when polyanions and polycations are mixed together in proper conditions of an aqueous solution. This mixing results in a phase separation of a polymer-rich, coacervate phase composed of a chain network held together via

  7. Low Molecular Weight pDMAEMA-block-pHEMA Block-Copolymers Synthesized via RAFT-Polymerization: Potential Non-Viral Gene Delivery Agents?

    Directory of Open Access Journals (Sweden)

    Thomas Kissel

    2011-03-01

    Full Text Available The aim of this study was to investigate non-viral pDNA carriers based on diblock-copolymers consisting of poly(2-(dimethyl aminoethyl methacrylate (pDMAEMA and poly(2-hydroxyethyl methacrylate (pHEMA. Specifically the block-lengths and molecular weights were varied to determine the minimal requirements for transfection. Such vectors should allow better transfection at acceptable toxicity levels and the entire diblock-copolymer should be suitable for renal clearance. For this purpose, a library of linear poly(2-(dimethyl aminoethyl methacrylate-block-poly(2-hydroxyl methacrylate (pDMAEMA-block-pHEMA copolymers was synthesized via RAFT (reversible addition-fragmentation chain transfer polymerization in a molecular weight (Mw range of 17–35.7 kDa and analyzed using 1H and 13C NMR (nuclear magnetic resonance, ATR (attenuated total reflectance, GPC (gel permeation chromatography and DSC (differential scanning calorimetry. Copolymers possessing short pDMAEMA-polycation chains were 1.4–9.7 times less toxic in vitro than polyethylenimine (PEI 25 kDa, and complexed DNA into polyplexes of 100–170 nm, favorable for cellular uptake. The DNA-binding affinity and polyplex stability against competing polyanions was comparable with PEI 25 kDa. The zeta-potential of polyplexes of pDMAEMA-grafted copolymers remained positive (+15–30 mV. In comparison with earlier reported low molecular weight homo pDMAEMA vectors, these diblock-copolymers showed enhanced transfection efficacy under in vitro conditions due to their lower cytotoxicity, efficient cellular uptake and DNA packaging. The homo pDMAEMA115 (18.3 kDa self-assembled with DNA into small positively charged polyplexes, but was not able to transfect cells. The grafting of 6 and 57 repeating units of pHEMA (0.8 and 7.4 kDa to pDMAEMA115 increased the transfection efficacy significantly, implying a crucial impact of pHEMA on vector-cell interactions. The intracellular trafficking, in vivo transfection

  8. Synthesis and characterization of titania nanotubes and gold nanoparticles nanocomposites for hydrogen production improvement

    Energy Technology Data Exchange (ETDEWEB)

    Galvao, Rhauane Almeida, E-mail: rhaugalvao@hotmail.com [Universidade Federal de Pernambuco (UFPE), Recife, PE(Brazil); Silva, Germana Michelle Medeiros e; Machado, Giovanna [Centro de Tecnologias Estrategicas do Nordeste, Recife, PE (Brazil)

    2016-07-01

    Full text: In the New Policies Scenario, world electricity demand increases by almost 80% over the period 2012-2040. According to this, the world will need to increase energy supply and cleanly-generated electricity. Besides renewable energy sources such as solar energy have a high cost, it can provide clean power. Because of this, it is of great interest to create new devices capable to absorb and convert solar into electrical energy. Titanium dioxide (TiO{sub 2}) is a great searched semiconductor for solar energy conversion because of its great stability and low cost, besides its low solar energy absorption (± 5% of solar spectrum). Sensitization with nanoparticles, such as gold (Au), is a good alternative to increase its efficiency. Using architectures such as nanotubes (NTs) and nanoparticles (NPs) is of interesting because of the unique properties achieved at these dimensions. To bind Au Nps into TiO{sub 2} NTs is a great challenge. Using self assembled thin films is a good option because of its operability. On this study, amorphous TiO{sub 2} NTs were synthesized by anodization of a Ti foil using an organic electrolyte with a set potential during 30 minutes. After this, the self-assembly method was used on the tubes using Poly(Allylamine Hydrochloride) (PAH) as polycation and Poly(Acrilic Acid) (PAA) as polyanion, completing 10 and 10.5. Then, the samples were immersed in a solution of Tetrachloroauric acid (HAuCl{sub 4}) at different pHs during 2 hours, lightly washed and submitted to UV-radiation during 24 hours. In order to make a comparison, it has been prepared samples without binds. At last, the samples were heat treated at 400°C during 3 hours to obtain TiO2 anatase phase. X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Diffuse Reflectance Spectroscopy characterized the samples. Finally, the hydrogen production was evaluated using a solar simulator and gas chromatography. The results show that the use of a bind is greatly favorable to

  9. Enhancing siRNA-based cancer therapy using a new pH-responsive activatable cell-penetrating peptide-modified liposomal system

    Directory of Open Access Journals (Sweden)

    Xiang B

    2017-03-01

    Full Text Available Bai Xiang,1,* Xue-Li Jia,1,* Jin-Long Qi,2 Li-Ping Yang,1 Wei-Hong Sun,1 Xiao Yan,1 Shao-Kun Yang,1 De-Ying Cao,1 Qing Du,1 Xian-Rong Qi3 1Department of Pharmaceutics, School of Pharmaceutical Sciences, 2Department of Pharmacology, Hebei Medical University, Shijiazhuang, Hebei, 3School of Pharmaceutical Sciences, Peking University, Beijing, China *These authors contributed equally to this work Abstract: As a potent therapeutic agent, small interfering RNA (siRNA has been exploited to silence critical genes involved in tumor initiation and progression. However, development of a desirable delivery system is required to overcome the unfavorable properties of siRNA such as its high degradability, molecular size, and negative charge to help increase its accumulation in tumor tissues and promote efficient cellular uptake and endosomal/lysosomal escape of the nucleic acids. In this study, we developed a new activatable cell-penetrating peptide (ACPP that is responsive to an acidic tumor microenvironment, which was then used to modify the surfaces of siRNA-loaded liposomes. The ACPP is composed of a cell-penetrating peptide (CPP, an acid-labile linker (hydrazone, and a polyanionic domain, including glutamic acid and histidine. In the systemic circulation (pH 7.4, the surface polycationic moieties of the CPP (polyarginine are “shielded” by the intramolecular electrostatic interaction of the inhibitory domain. When exposed to a lower pH, a common property of solid tumors, the ACPP undergoes acid-catalyzed breakage at the hydrazone site, and the consequent protonation of histidine residues promotes detachment of the inhibitory peptide. Subsequently, the unshielded CPP would facilitate the cellular membrane penetration and efficient endosomal/lysosomal evasion of liposomal siRNA. A series of investigations demonstrated that once exposed to an acidic pH, the ACPP-modified liposomes showed elevated cellular uptake, downregulated expression of polo

  10. Enhanced activity of carbosilane dendrimers against HIV when combined with reverse transcriptase inhibitor drugs: searching for more potent microbicides

    Directory of Open Access Journals (Sweden)

    Vacas-Córdoba E

    2014-07-01

    Full Text Available Enrique Vacas-Córdoba,1–3 Marta Galán,3,4 Francisco J de la Mata,3,4 Rafael Gómez,3,4 Marjorie Pion,1–3 M Ángeles Muñoz-Fernández1–3 1Laboratorio InmunoBiología Molecular, Hospital General Universitario Gregorio Marañón, Madrid, Spain; 2Instituto de Investigación Sanitaria del Gregorio Marañón, Madrid, Spain; 3Networking Research Center on Bioengineering, Biomaterials and Nanomedicine, (CIBER-BBN, Madrid, Spain; 4Dendrimers for Biomedical Applications Group (BioInDen, University of Alcalá, Madrid, Spain Abstract: Self-administered topical microbicides or oral preexposure prophylaxis could be very helpful tools for all risk groups to decrease the human immunodeficiency virus (HIV-1 infection rates. Up until now, antiretrovirals (ARVs have been the most advanced microbicide candidates. Nevertheless, the majority of clinical trials has failed in HIV-1 patients. Nanotechnology offers suitable approaches to develop novel antiviral agents. Thereby, new nanosystems, such as carbosilane dendrimers, have been shown to be safe and effective compounds against HIV with great potential as topical microbicides. In addition, because most of the attempts to develop effective topical microbicides were unsuccessful, combinatorial strategies could be a valid approach when designing new microbicides. We evaluated various combinations of anionic carbosilane dendrimers with sulfated (G3-S16 and naphthyl sulfonated (G2-NF16 ended groups with different ARVs against HIV-1 infection. The G3-S16 and G2-NF16 dendrimers showed a synergistic or additive activity profile with zidovudine, efavirenz, and tenofovir in the majority of the combinations tested against the X4 and R5 tropic HIV-1 in cell lines, as well as in human primary cells. Therefore, the combination of ARVs and polyanionic carbosilane dendrimers enhances the antiviral potency of the individual compounds, and our findings support further clinical research on combinational approaches as

  11. Spontaneous HIT syndrome post-knee replacement surgery with delayed recovery of thrombocytopenia: a case report and literature review.

    Science.gov (United States)

    Poudel, Dilli Ram; Ghimire, Sushil; Dhital, Rashmi; Forman, Daniel A; Warkentin, Theodore E

    2017-09-01

    Recently published reports have established a heparin-induced thrombocytopenia (HIT)-mimicking thromboembolic disorder without proximate heparin exposure, called spontaneous HIT syndrome. Although the pathophysiology remains unclear, anti-platelet factor 4 (PF4)/heparin antibodies possibly triggered by exposure to knee cartilage glycosaminoglycans or other non-heparin polyanions found on bacterial surfaces and nucleic acids have been postulated. We present a 53-year-old female receiving antithrombotic prophylaxis with aspirin following right total knee replacement surgery (without perioperative or any previous lifetime heparin exposure) who acutely presented with high-risk pulmonary embolism (PE) and right great saphenous vein thrombophlebitis on postoperative day (POD) 14; her platelet count at presentation was 13 × 10 9 /L. Prior to diagnostic consideration of spontaneous HIT syndrome, the patient briefly received unfractionated heparin (UFH) and one dose of enoxaparin. The patient's serum tested strongly positive for anti-PF4/heparin antibodies by two different PF4-dependent enzyme-linked immunosorbent assays (ELISAs) and by serotonin release assay (SRA). Failure of fondaparinux anticoagulation (persisting HIT-associated disseminated intravascular coagulation) prompted switching to argatroban. Severe thrombocytopenia persisted (platelet count nadir, 12 × 10 9 /L, on POD21), and 9 days after starting argatroban symptomatic right leg deep-vein thrombosis (DVT) occurred, prompting switch to rivaroxaban. Thereafter, her course was uneventful, although platelet count recovery was prolonged, reaching 99 × 10 9 /L by POD45 and 199 × 10 9 /L by POD79. The patient's serum elicited strong serotonin release in the absence of heparin (seen even with 1/32 serum dilution) that was enhanced by pharmacological concentrations of UFH (0.1 and 0.3 IU/mL) and fondaparinux (0.1-1.2 μg/mL, i.e., in vitro fondaparinux "cross-reactivity"). Ultimately, platelet count recovery was

  12. Phosphide oxides RE2AuP2O (RE = La, Ce, Pr, Nd): synthesis, structure, chemical bonding, magnetism, and 31P and 139La solid state NMR.

    Science.gov (United States)

    Bartsch, Timo; Wiegand, Thomas; Ren, Jinjun; Eckert, Hellmut; Johrendt, Dirk; Niehaus, Oliver; Eul, Matthias; Pöttgen, Rainer

    2013-02-18

    Polycrystalline samples of the phosphide oxides RE(2)AuP(2)O (RE = La, Ce, Pr, Nd) were obtained from mixtures of the rare earth elements, binary rare earth oxides, gold powder, and red phosphorus in sealed silica tubes. Small single crystals were grown in NaCl/KCl fluxes. The samples were studied by powder X-ray diffraction, and the structures were refined from single crystal diffractometer data: La(2)AuP(2)O type, space group C2/m, a = 1515.2(4), b = 424.63(8), c = 999.2(2) pm, β = 130.90(2)°, wR2 = 0.0410, 1050 F(2) values for Ce(2)AuP(2)O, and a = 1503.6(4), b = 422.77(8), c = 993.0(2) pm, β = 130.88(2)°, wR2 = 0.0401, 1037 F(2) values for Pr(2)AuP(2)O, and a = 1501.87(5), b = 420.85(5), c = 990.3(3) pm, β = 131.12(1)°, wR2 = 0.0944, 1143 F(2) values for Nd(2)AuP(2)O with 38 variables per refinement. The structures are composed of [RE(2)O](4+) polycationic chains of cis-edge-sharing ORE(4/2) tetrahedra and polyanionic strands [AuP(2)](4-), which contain gold in almost trigonal-planar phosphorus coordination by P(3-) and P(2)(4-) entities. The isolated phosphorus atoms and the P(2) pairs in La(2)AuP(2)O could clearly be distinguished by (31)P solid state NMR spectroscopy and assigned on the basis of a double quantum NMR technique. Also, the two crystallographically inequivalent La sites could be distinguished by static (139)La NMR in conjunction with theoretical electric field gradient calculations. Temperature-dependent magnetic susceptibility measurements show diamagnetic behavior for La(2)AuP(2)O. Ce(2)AuP(2)O and Pr(2)AuP(2)O are Curie-Weiss paramagnets with experimental magnetic moments of 2.35 and 3.48 μ(B) per rare earth atom, respectively. Their solid state (31)P MAS NMR spectra are strongly influenced by paramagnetic interactions. Ce(2)AuP(2)O orders antiferromagnetically at 13.1(5) K and shows a metamagnetic transition at 11.5 kOe. Pr(2)AuP(2)O orders ferromagnetically at 7.0 K.

  13. Solution phase and membrane immobilized iron-based free radical reactions: Fundamentals and applications for water treatment

    Science.gov (United States)

    Lewis, Scott Romak

    Membrane-based separation processes have been used extensively for drinking water purification, wastewater treatment, and numerous other applications. Reactive membranes synthesized through functionalization of the membrane pores offer enhanced reactivity due to increased surface area at the polymer-solution interface and low diffusion limitations. Oxidative techniques utilizing free radicals have proven effective for both the destruction of toxic organics and non-environmental applications. Most previous work focuses on reactions in the homogeneous phase; however, the immobilization of reactants in membrane pores offers several advantages. The use of polyanions immobilized in a membrane or chelates in solution prevents ferric hydroxide precipitation at near-neutral pH, a common limitation of iron(Fe(II/III))-catalyzed hydrogen peroxide (H 2O2) decomposition. The objectives of this research are to develop a membrane-based platform for the generation of free radicals, degrade toxic organic compounds using this and similar solution-based reactions, degrade toxic organic compounds in droplet form, quantify hydroxyl radical production in these reactions, and develop kinetic models for both processes. In this study, a functionalized membrane containing poly(acrylic acid) (PAA) was used to immobilize iron ions and conduct free radical reactions by permeating H2O2 through the membrane. The membrane's responsive behavior to pH and divalent cations was investigated and modeled. The conversion of Fe(II) to Fe(III) in the membrane and its effect on the decomposition of hydrogen peroxide were monitored and used to develop kinetic models for predicting H2O2 decomposition in these systems. The rate of hydroxyl radical production, and hence contaminant degradation can be varied by changing the residence time, H2O2 concentration, and/or iron loading. Using these membrane-immobilized systems, successful removal of toxic organic compounds, such as pentachlorophenol (PCP), from water

  14. Two supramolecular complexes based on polyoxometalates and Co-EDTA units via covalent connection or non-covalent interaction

    Energy Technology Data Exchange (ETDEWEB)

    Teng, Chunlin; Xiao, Hanxi [Key Laboratory of Theoretical Organic Chemistry and Functional Molecule for Ministry of Education, Hunan University of Science and Technology, Xiangtan 411201 (China); Cai, Qing [Chemistry Department, City University of New York, New York, NY 10016 (United States); Tang, Jianting; Cai, Tiejun [Key Laboratory of Theoretical Organic Chemistry and Functional Molecule for Ministry of Education, Hunan University of Science and Technology, Xiangtan 411201 (China); Deng, Qian, E-mail: dengqian10502@163.com [Key Laboratory of Theoretical Organic Chemistry and Functional Molecule for Ministry of Education, Hunan University of Science and Technology, Xiangtan 411201 (China)

    2016-11-15

    Two new 3D network organic-inorganic hybrid supramolecular complexes ([Na{sub 6}(CoEDTA){sub 2}(H{sub 2}O){sub 13}]·(H{sub 2}SiW{sub 12}O{sub 40})·xH{sub 2}O)n (1) and [CoH{sub 4}EDTA(H{sub 2}O)]{sub 2}(SiW{sub 12}O{sub 40})·15H{sub 2}O (2) (H{sub 4}EDTA=Ethylenediamine tetraacetic acid) have been successfully synthesized by solution method, and characterized by infrared spectrum (IR), thermogravimetric-differential thermal analysis (TG-DTA), cyclic voltammetry (CV) and single{sup −}crystal X-ray diffraction (XRD). Both of the complexes are the supramolecules, but with different liking mode, they are two representative models of supramolecule. complex (1) is a 3D infinite network supramolecular coordination polymer with a rare multi-metal sturcture of sodium-cobalt-containing, which is mainly linked through coordinate-covalent bonds. While complex (2) is normal supramolecule, which linked by non-covalent interactions, such as H-bonding interaction, electrostatic interaction and van der waals force. Both of complex (1) and (2) exhibit good catalytic activities for catalytic oxidation of methanol, when the initial concentration of methanol is 3.0 g m{sup −3}, flow rate is 10 mL min{sup −1}, and the quality of catalyst is 0.2 g, for complex (1) and complex (2) the maximum elimination rates of methanol are 85% (150 °C) and 92% (120 °C), respectively. - Graphical abstract: Two new organic-inorganic hybrid supramolecular complexes based on Co-EDTA, and Keggin polyanions have been successfully synthesized with different pH value by solution method. They are attributed to two representative models of supramolecule. Complex(1) is an infinite coordination polymer with a rare multi-metal sturcture of sodium-cobalt-containing, which is mainly linked through covalent bonds. Complex (2) is a normal supramolecule, which linked by non-covalent interactions of H-bonding interaction, electrostatic interaction and van der waals force. - Highlights: • Two supramolecules

  15. Collective epithelial cell sheet adhesion and migration on polyelectrolyte multilayers with uniform and gradients of compliance

    International Nuclear Information System (INIS)

    Martinez, Jessica S.; Schlenoff, Joseph B.; Keller, Thomas C.S.

    2016-01-01

    Polyelectrolyte multilayers (PEMUs) are tunable thin films that could serve as coatings for biomedical implants. PEMUs built layer by layer with the polyanion poly(acrylic acid) (PAA) modified with a photosensitive 4-(2-hydroxyethoxy) benzophenone (PAABp) group and the polycation poly(allylamine hydrochloride) (PAH) are mechanically tunable by UV irradiation, which forms covalent bonds between the layers and increases PEMU stiffness. PAH-terminated PEMUs (PAH-PEMUs) that were uncrosslinked, UV-crosslinked to a uniform stiffness, or UV-crosslinked with an edge mask or through a neutral density optical gradient filter to form continuous compliance gradients were used to investigate how differences in PEMU stiffness affect the adhesion and migration of epithelial cell sheets from scales of the fish Poecilia sphenops (Black Molly) and Carassius auratus (Comet Goldfish). During the progressive collective cell migration, the edge cells (also known as ‘leader’ cells) in the sheets on softer uncrosslinked PEMUs and less crosslinked regions of the gradient formed more actin filaments and vinculin-containing adherens junctions and focal adhesions than formed in the sheet cells on stiffer PEMUs or glass. During sheet migration, the ratio of edge cell to internal cell (also known as ‘follower’ cells) motilities were greater on the softer PEMUs than on the stiffer PEMUs or glass, causing tension to develop across the sheet and periods of retraction, during which the edge cells lost adhesion to the substrate and regions of the sheet retracted toward the more adherent internal cell region. These retraction events were inhibited by the myosin II inhibitor Blebbistatin, which reduced the motility velocity ratios to those for sheets on the stiffer PEMUs. Blebbistatin also caused disassembly of actin filaments, reorganization of focal adhesions, increased cell spreading at the leading edge, as well as loss of edge cell-cell connections in epithelial cell sheets on all

  16. Barium aluminides BaxAl5(x=3,3.5,4)

    International Nuclear Information System (INIS)

    Jehle, Michael; Scherer, Harald; Wendorff, Marco; Roehr, Caroline

    2009-01-01

    Three aluminides of the series Ba x Al 5 (x=3,3.5,4) were synthesized from stoichiometric ratios of the elements in Ta crucibles. The crystal structure of the new compound Ba 7 Al 10 was determined using single crystal X-ray data (space group R3-barm, a=604.23(9), c=4879.0(12)pm, Z=3, R1=0.0325). The compound exhibits Al Kagome (3.6.3.6.) nets in which half of the triangles form the basis of trigonal bipyramids Al 5 . The apical Al are thus three-bonded assuming a charge of -2 ( 27 Al-NMR chemical shift δ=660pm), whereas the Al atoms of the basal triangle (i.e. of the Kagome net) are four-bonded and thus of formal charge -1(δ=490ppm). The total charge of the anion is thus exactly compensated by the Ba cations, i.e. the compound can be interpreted as an electron precise Zintl phase, exhibiting a distinct pseudo-band gap at the Fermi level of the calculated tDOS. According to the total formula, the structure displays a combination the stacking sequences of Ba 3 Al 5 and Ba 4 Al 5 , the structures of which have been redetermined with current methods (both hexagonal with space group P6 3 /mmc; Ba 3 Al 5 : a=606.55(7), c=1461.8(2)pm, Z=2, R1=0.0239; Ba 4 Al 5 : a=609.21(7), c=1775.8(3)pm, Z=2, R1=0.0300). These three compounds with slightly different electron counts but similar polyanions allow to compare the bond lengths, the electronic structures and the overall bonding situation in dependence of positive or negative deviation of the electron count in relation to the novel formally electron precise Zintl compound Ba 7 Al 10 . - Al 5 layers of Kagome nets in the new binary electron precise Zintl compound Ba 3.5 Al 5 , also found in Ba 3 Al 5 and Ba 4 Al 5 .

  17. Amorphous, Smart, and Bioinspired Polyphosphate Nano/Microparticles: A Biomaterial for Regeneration and Repair of Osteo-Articular Impairments In-Situ

    Directory of Open Access Journals (Sweden)

    Werner E. G. Müller

    2018-01-01

    Full Text Available Using femur explants from mice as an in vitro model, we investigated the effect of the physiological polymer, inorganic polyphosphate (polyP, on differentiation of the cells of the bone marrow in their natural microenvironment into the osteogenic and chondrogenic lineages. In the form of amorphous Ca-polyP nano/microparticles, polyP retains its function to act as both an intra- and extracellular metabolic fuel and a stimulus eliciting morphogenetic signals. The method for synthesis of the nano/microparticles with the polyanionic polyP also allowed the fabrication of hybrid particles with the bisphosphonate zoledronic acid, a drug used in therapy of bone metastases in cancer patients. The results revealed that the amorphous Ca-polyP particles promote the growth/viability of mesenchymal stem cells, as well as the osteogenic and chondrogenic differentiation of the bone marrow cells in rat femur explants, as revealed by an upregulation of the expression of the transcription factors SOX9 (differentiation towards osteoblasts and RUNX2 (chondrocyte differentiation. In parallel to this bone anabolic effect, incubation of the femur explants with these particles significantly reduced the expression of the gene encoding the osteoclast bone-catabolic enzyme, cathepsin-K, while the expression of the tartrate-resistant acid phosphatase remained unaffected. The gene expression data were supported by the finding of an increased mineralization of the cells in the femur explants in response to the Ca-polyP particles. Finally, we show that the hybrid particles of polyP complexed with zoledronic acid exhibit both the cytotoxic effect of the bisphosphonate and the morphogenetic and mineralization inducing activity of polyP. Our results suggest that the Ca-polyP nano/microparticles are not only a promising scaffold material for repairing long bone osteo-articular damages but can also be applied, as a hybrid with zoledronic acid, as a drug delivery system for

  18. Complex cubic metallides AM{sub ∝6} (A=Ca, Sr; M=Zn, Cd, Hg). Synthesis, crystal chemistry and chemical bonding

    Energy Technology Data Exchange (ETDEWEB)

    Schwarz, Michael; Wendorff, Marco; Roehr, Caroline [Freiburg Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie

    2017-09-01

    In a systematic synthetic, crystallographic and bond theoretical study, the stability ranges as well as the distribution of the isoelectronic late d-block elements Zn, Cd and Hg (M) in the polyanions of the YCd{sub 6}-type phases (Ca/Sr)Cd{sub 6} have been investigated. Starting from Ca(Cd/Hg){sub 6}, 12-30% of the M atoms can be substituted by Zn, which gradually occupies the center of the empty cubes. In all ternary compounds, smaller/less electronegative Zn/Cd atoms occupy the disordered tetrahedra explaining the lack of the YCd{sub 6}-type for pure mercurides. Along the section SrCd{sub 6}-SrHg{sub 6}, the ordered Eu{sub 4}Cd{sub 25}-type is formed (Sr{sub 4}Cd{sub 16.1}Hg{sub 8.9}: cF1392, Fd anti 3, a=3191.93(5) pm, R1=0.0404). Besides, two new complex cubic Ca phases appear at increased Zn proportion: Ca{sub 2}Zn{sub 5.1}Cd{sub 5.8}, which exhibits a nearly complete site preference of Zn and Cd, crystallizes in the rare cubic Mg{sub 2}Zn{sub 11}-type structure (cP39-δ, Pm anti 3, a=918.1(1) pm, R1=0.0349). In the Ca-Hg system, an increased Zn proportion yielded the new compound CaZn{sub 1.31}Hg{sub 3.69} (cF480, F anti 43m, a=2145.43(9) pm, R1=0.0572), with a complex cubic structure closely related to Ba{sub 20}Hg{sub 103}. All structures, which are commonly described using nested polyhedra around high-symmetric sites, are alternatively described in accordance with the calculated electron densities and charge distribution: building blocks are face-sharing [M{sub 4}] tetrahedra (star polyhedra such as TS, IS, OS), each with a cage-critical point in its center, and [M{sub 8}] cubes (deformed TS), which are either empty, distorted or filled. The M element distribution in the anion is determined by size criteria and the difference in electronegativity, which induces a preferred formation of heteroatomic polar bonds.

  19. La{sub 3}Cu{sub 4}P{sub 4}O{sub 2} and La{sub 5}Cu{sub 4}P{sub 4}O{sub 4}Cl{sub 2}. Synthesis, structure and {sup 31}P solid state NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Bartsch, Timo; Eul, Matthias; Poettgen, Rainer [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie; Benndorf, Christopher; Eckert, Hellmut [Muenster Univ. (Germany). Inst. fuer Physikalische Chemie; Sao Paulo Univ., Sao Carlos, SP (Brazil). Inst. of Physics

    2016-04-01

    The phosphide oxides La{sub 3}Cu{sub 4}P{sub 4}O{sub 2} and La{sub 5}Cu{sub 4}P{sub 4}O{sub 4}Cl{sub 2} were synthesized from lanthanum, copper(I) oxide, red phosphorus, and lanthanum(III) chloride through a ceramic technique. Single crystals can be grown in a NaCl/KCl flux. Both structures were refined from single crystal X-ray diffractometer data: I4/mmm, a = 403.89(4), c = 2681.7(3) pm, wR2 = 0.0660, 269 F{sup 2} values, 19 variables for La{sub 3}Cu{sub 4}P{sub 4}O{sub 2} and a = 407.52(5), c = 4056.8(7) pm, wR2 = 0.0905, 426 F{sup 2} values, 27 variables for La{sub 5}Cu{sub 4}P{sub 4}O{sub 4}Cl{sub 2}. Refinement of the occupancy parameters revealed full occupancy for the oxygen sites in both compounds. The structures are composed of cationic (La{sub 2}O{sub 2}){sup 2+} layers and covalently bonded (Cu{sub 4}P{sub 4}){sup 5-} polyanionic layers with metallic characteristics, and an additional La{sup 3+} between two adjacent (Cu{sub 4}P{sub 4}){sup 5-} layers. The structure of La{sub 5}Cu{sub 4}P{sub 4}O{sub 4}Cl{sub 2} comprises two additional LaOCl slabs per unit cell. Temperature-dependent magnetic susceptibility studies revealed Pauli paramagnetism. The phosphide substructure of La{sub 3}Cu{sub 4}P{sub 4}O{sub 2} was studied by {sup 31}P solid state NMR spectroscopy. By using a suitable dipolar re-coupling approach the two distinct resonances belonging to the P{sub 2}{sup 4-} and the P{sup 3-} units could be identified.

  20. Collective epithelial cell sheet adhesion and migration on polyelectrolyte multilayers with uniform and gradients of compliance

    Energy Technology Data Exchange (ETDEWEB)

    Martinez, Jessica S. [Department of Biological Science, Florida State University, Tallahassee, FL 32306 (United States); Schlenoff, Joseph B. [Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL 32306 (United States); Keller, Thomas C.S., E-mail: tkeller@bio.fsu.edu [Department of Biological Science, Florida State University, Tallahassee, FL 32306 (United States)

    2016-08-01

    Polyelectrolyte multilayers (PEMUs) are tunable thin films that could serve as coatings for biomedical implants. PEMUs built layer by layer with the polyanion poly(acrylic acid) (PAA) modified with a photosensitive 4-(2-hydroxyethoxy) benzophenone (PAABp) group and the polycation poly(allylamine hydrochloride) (PAH) are mechanically tunable by UV irradiation, which forms covalent bonds between the layers and increases PEMU stiffness. PAH-terminated PEMUs (PAH-PEMUs) that were uncrosslinked, UV-crosslinked to a uniform stiffness, or UV-crosslinked with an edge mask or through a neutral density optical gradient filter to form continuous compliance gradients were used to investigate how differences in PEMU stiffness affect the adhesion and migration of epithelial cell sheets from scales of the fish Poecilia sphenops (Black Molly) and Carassius auratus (Comet Goldfish). During the progressive collective cell migration, the edge cells (also known as ‘leader’ cells) in the sheets on softer uncrosslinked PEMUs and less crosslinked regions of the gradient formed more actin filaments and vinculin-containing adherens junctions and focal adhesions than formed in the sheet cells on stiffer PEMUs or glass. During sheet migration, the ratio of edge cell to internal cell (also known as ‘follower’ cells) motilities were greater on the softer PEMUs than on the stiffer PEMUs or glass, causing tension to develop across the sheet and periods of retraction, during which the edge cells lost adhesion to the substrate and regions of the sheet retracted toward the more adherent internal cell region. These retraction events were inhibited by the myosin II inhibitor Blebbistatin, which reduced the motility velocity ratios to those for sheets on the stiffer PEMUs. Blebbistatin also caused disassembly of actin filaments, reorganization of focal adhesions, increased cell spreading at the leading edge, as well as loss of edge cell-cell connections in epithelial cell sheets on all

  1. Assessment of topical microbicides to prevent HIV-1 transmission: concepts, testing, lessons learned.

    Science.gov (United States)

    Friend, David R; Kiser, Patrick F

    2013-09-01

    The development of topically applied products capable of preventing vaginal and rectal transmission of HIV-1 has been on-going for nearly 20 years. Despite this, only one clinical trial has demonstrated protection against sexual transmission of HIV-1 in women. This review covers the development of microbicides, also referred to as topical pre-exposure prophylaxis (PrEP), through three stages. The first stage focused on nonspecific agents, including surfactants such as nonoxynol-9 (N-9), to prevent HIV-1 transmission. Unfortunately, N-9 enhanced susceptibility to sexual transmission of HIV-1 when evaluated for efficacy. Soon thereafter, other nonspecific agents (polyanions) were quickly moved into large efficacy trials. Due to a lack of coordination among investigators and funders, a large investment was made in a class of compounds shown ultimately to be ineffective, although poor adherence may have contributed to these findings. The second stage involved the assessment of the antiretroviral drug tenofovir, formulated as a vaginal gel, which was found to be modestly effective in a Phase IIb trial (CAPRISA-004) when dosed in a coitally-dependent manner. In another Phase IIb trial, VOICE (MTN-003), tenofovir gel was found to be ineffective when dosed once-daily in a coitally-independent manner. Based on pharmacokinetic data, it was concluded the participants were poorly adherent to this dosing regimen, leading to a lack of efficacy. Tenofovir gel is currently in a Phase III safety and efficacy trial in South Africa (FACTS-001), using the coitally-dependent dosing regimen employed in CAPRISA-004. We are now in the third stage of microbicide research. The antiretroviral drug dapivirine is currently in two Phase III safety and efficacy studies formulated as a vaginal ring. It is hoped that the once-monthly dosing regimen will lead to higher adherence than found in the VOICE study. It is now clear that product adherence could be the greatest challenge to demonstrating

  2. Development of a local anesthetic lidocaine-loaded redox-active injectable gel for postoperative pain management.

    Science.gov (United States)

    Nagasaki, Yukio; Mizukoshi, Yutaro; Gao, Zhenyu; Feliciano, Chitho P; Chang, Kyungho; Sekiyama, Hiroshi; Kimura, Hiroyuki

    2017-07-15

    Although local anesthesia is commonly applied for pain relief, there are several issues such as its short duration of action and low effectiveness at the areas of inflammation due to the acidic pH. The presence of excessive amount of reactive oxygen species (ROS) is known to induce inflammation and aggravate pain. To resolve these issues, we developed a redox-active injectable gel (RIG) with ROS-scavenging activity. RIG was prepared by mixing polyamine-b-poly(ethylene glycol)-b-polyamine with nitroxide radical moieties as side chains on the polyamine segments (PMNT-b-PEG-b-PMNT) with a polyanion, which formed a flower-type micelle via electrostatic complexation. Lidocaine could be stably incorporated in its core. When the temperature of the solution was increased to 37°C, the PIC-type flower micelle transformed to gel. The continuous release of lidocaine from the gel was observed for more than three days, without remarkable initial burst, which is probably owing to the stable entrapment of lidocaine in the PIC core of the gel. We evaluated the analgesic effect of RIG in carrageenan-induced arthritis mouse model. Results showed that lidocaine-loaded RIG has stronger and longer analgesic effect when administered in inflamed areas. In contrast, while the use of non-complexed lidocaine did not show analgesic effect one day after its administration. Note that no effect was observed when PIC-type flower micelle without ROS-scavenging ability was used. These findings suggest that local anesthetic-loaded RIG can effectively reduce the number of injection times and limit the side effects associated with the use of anti-inflammatory drugs for postoperative pain management. 1. We have been working on nanomaterials, which effectively eliminate ROS, avoiding dysfunction of mitochondria in healthy cells. 2. We designed redox injectable gel using polyion complexed flower type micelle, which can eliminates ROS locally. 3. We could prepare local anesthesia-loaded redox injectable

  3. TPP-dendrimer nanocarriers for siRNA delivery to the pulmonary epithelium and their dry powder and metered-dose inhaler formulations.

    Science.gov (United States)

    Bielski, Elizabeth; Zhong, Qian; Mirza, Hamad; Brown, Matthew; Molla, Ashura; Carvajal, Teresa; da Rocha, Sandro R P

    2017-07-15

    The regulation of genes utilizing the RNA interference (RNAi) mechanism via the delivery of synthetic siRNA has great potential in the treatment of a variety of lung diseases. However, the delivery of siRNA to the lungs is challenging due to the poor bioavailability of siRNA when delivered intraveneously, and difficulty in formulating and maintaining the activity of free siRNA when delivered directly to the lungs using inhalation devices. The use of non-viral vectors such as cationic dendrimers can help enhance the stability of siRNA and its delivery to the cell cytosol. Therefore, in this work, we investigate the ability of a triphenylphosphonium (TPP) modified generation 4 poly(amidoamine) (PAMAM) dendrimer (G4NH 2 -TPP) to enhance the in vitro transfection efficiency of siRNA in a model of the pulmonary epithelium and their aerosol formulations in pressurized metered dose inhalers (pMDIs) and dry powder inhalers (DPIs). Complexes of siRNA and G4NH 2 -TPP were prepared with varying TPP densities and increasing N/P ratios. The complexation efficiency was modulated by the presence of the TPP on the dendrimer surface, allowing for a looser complexation compared to unmodified dendrimer as determined by gel electrophoresis and polyanion competition assay. An increase in TPP density and N/P ratio led to an increase in the in vitro gene knockdown of stably green fluorescent protein (eGFP) expressing lung alveolar epithelial (A549) cells. G4NH 2 -12TPP dendriplexes (G4NH 2 PAMAM dendrimers containing 12 TPP molecules on the surface complexed with siRNA) at N/P ratio 30 showed the highest in vitro gene knockdown efficiency. To assess the potential of TPP-dendriplexes for pulmonary use, we also developed micron particle technologies for both pMDIs and DPIs and determined their aerosol characteristics utilizing an Andersen Cascade Impactor (ACI). Mannitol microparticles encapsulating 12TPP-dendriplexes were shown to be effective in producing aerosols suitable for deep lung

  4. The new barium mercuride BaHg6 and ternary indium and gallium derivatives

    International Nuclear Information System (INIS)

    Wendorff, Marco; Röhr, Caroline

    2013-01-01

    show that indium as well as gallium are the positively charged bonding partners inside the Hg/M polyanions.

  5. Three inorganic-organic hybrid complexes based on isopolymolybdate and derivatives of 1H-4-nitroimidazole

    Science.gov (United States)

    Zhang, Xiaoyu; Xi, Rui; Yin, Sulu; Cao, Xiaoran; Zhang, Yongliang; Lin, Ling; Chen, Rui; Wu, Hua

    2018-02-01

    Three inorganic-organic diverse CuI motifs of [CuI(bnip)]2(Mo6O19) (1), CuI4(bnib)3(β-Mo8O26)(H2O) (2) and [CuI(bnih)]2(Mo6O19)·H2O (3) [bnip = 1,3-bis(4-nitro-1H-imidazol-1-yl)propane, bnib = 1,4-bis(4-nitro-1H-imidazol-1-yl)butane, and bnih = 1,6-bis(4-nitro-1H-imidazol-1-yl)hexane] based on three diverse flexible ligands and isopolyoxomolybdate clusters have been successfully synthesized under solvothermal conditions at different pH values and ratio of the solvents. Their structures have been characterized by single-crystal X-ray diffraction analyses, infrared spectra (IR) and elemental analyses. For compound 1, the CuI ions are linked by bnip ligands to form a 2D 44 cationic layer, the 2D layers are packed in offset fashions through C-H···O hydrogen bonding interactions to generate a 3D supramolecular network with 1D channels, and the isolated [Mo6O19]2- polyanions are located in the channels. In compound 2, three bnib ligands are brigded by four CuI ions to form a unique unit of Cu4(binb)3(H2O)2, and the units are connected by Mo8O264- anions to generate an infinite 1D branched chain, which are further bridged by hydrogen bonding interactions to form a 2D supramolecular structure. In compound 3, two types of -Cu-bnih-Cu- chains are crossed each other to assemble a 3D supramolecular framework with 1D cationic channel by the hydrogen bonding interactions, and the channels are occupied by Mo6O192- anions. Furthermore, the thermal stabilities, power X-ray diffraction, the photoluminescent properties of compounds 1-3 and the electrochemical properties of compounds 1 and 2 have been also investigated.

  6. Clinical use of vaginal or rectally applied microbicides in patients suffering from HIV/AIDS

    Directory of Open Access Journals (Sweden)

    Gupta SK

    2013-10-01

    Full Text Available Satish Kumar Gupta, Nutan Reproductive Cell Biology Laboratory, National Institute of Immunology, New Delhi, India Abstract: Microbicides, primarily used as topical pre-exposure prophylaxis, have been proposed to prevent sexual transmission of HIV. This review covers the trends and challenges in the development of safe and effective microbicides to prevent sexual transmission of HIV. Initial phases of microbicide development used such surfactants as nonoxynol-9 (N-9, C13G, and sodium lauryl sulfate, aiming to inactivate the virus. Clinical trials of microbicides based on N-9 and C31G failed to inhibit sexual transmission of HIV. On the contrary, N-9 enhanced susceptibility to sexual transmission of HIV-1. Subsequently, microbicides based on polyanions and a variety of other compounds that inhibit the binding, fusion, or entry of virus to the host cells were evaluated for their efficacy in different clinical setups. Most of these trials failed to show either safety or efficacy for prevention of HIV transmission. The next phase of microbicide development involved antiretroviral drugs. Microbicide in the form of 1% tenofovir vaginal gel when tested in a Phase IIb trial (CAPRISA 004 in a coitally dependent manner revealed that tenofovir gel users were 39% less likely to become HIV-infected compared to placebo control. However, in another trial (VOICE MTN 003, tenofovir gel used once daily in a coitally independent mode failed to show any efficacy to prevent HIV infection. Tenofovir gel is currently in a Phase III safety and efficacy trial in South Africa (FACTS 001 employing a coitally dependent dosing regimen. Further, long-acting microbicide-delivery systems (vaginal ring for slow release of such antiretroviral drugs as dapivirine are also undergoing clinical trials. Discovering new markers as correlates of protective efficacy, novel long-acting delivery systems with improved adherence in the use of microbicides, discovering new compounds

  7. Structural and functional characterization of the product of disease-related factor H gene conversion.

    Science.gov (United States)

    Herbert, Andrew P; Kavanagh, David; Johansson, Conny; Morgan, Hugh P; Blaum, Bärbel S; Hannan, Jonathan P; Barlow, Paul N; Uhrín, Dušan

    2012-03-06

    Numerous complement factor H (FH) mutations predispose patients to atypical hemolytic uremic syndrome (aHUS) and other disorders arising from inadequately regulated complement activation. No unifying structural or mechanistic consequences have been ascribed to these mutants beyond impaired self-cell protection. The S1191L and V1197A mutations toward the C-terminus of FH, which occur in patients singly or together, arose from gene conversion between CFH encoding FH and CFHR1 encoding FH-related 1. We show that neither single nor double mutations structurally perturbed recombinant proteins consisting of the FH C-terminal modules, 19 and 20 (FH19-20), although all three FH19-20 mutants were poor, compared to wild-type FH19-20, at promoting hemolysis of C3b-coated erythrocytes through competition with full-length FH. Indeed, our new crystal structure of the S1191L mutant of FH19-20 complexed with an activation-specific complement fragment, C3d, was nearly identical to that of the wild-type FH19-20:C3d complex, consistent with mutants binding to C3b with wild-type-like affinity. The S1191L mutation enhanced thermal stability of module 20, whereas the V1197A mutation dramatically decreased it. Thus, although mutant proteins were folded at 37 °C, they differ in conformational rigidity. Neither single substitutions nor double substitutions increased measurably the extent of FH19-20 self-association, nor did these mutations significantly affect the affinity of FH19-20 for three glycosaminoglycans, despite critical roles of module 20 in recognizing polyanionic self-surface markers. Unexpectedly, FH19-20 mutants containing Leu1191 self-associated on a heparin-coated surface to a higher degree than on surfaces coated with dermatan or chondroitin sulfates. Thus, potentially disease-related functional distinctions between mutants, and between FH and FH-related 1, may manifest in the presence of specific glycosaminoglycans.

  8. Defibrotide, a polydisperse mixture of single-stranded phosphodiester oligonucleotides with lifesaving activity in severe hepatic veno-occlusive disease: clinical outcomes and potential mechanisms of action.

    Science.gov (United States)

    Kornblum, Noah; Ayyanar, Kanyalakshmi; Benimetskaya, Luba; Richardson, Paul; Iacobelli, Massimo; Stein, C A

    2006-01-01

    (LPS)-induced tissue factor (TF) expression. However, despite the fact the DF is composed of oligonucleotides, its mechanism of action, which at the present time is unclear, is not related to Watson-Crick base pair-dependent downregulation of gene expression but is rather likely a result of its polyanionic nature.

  9. Endothelium-dependent relaxation induced by cathepsin G in porcine pulmonary arteries

    Science.gov (United States)

    Glusa, Erika; Adam, Christine

    2001-01-01

    Serine proteinases elicit profound cellular effects in various tissues mediated by activation of proteinase-activated receptors (PAR). In the present study, we investigated the vascular effects of cathepsin G, a serine proteinase that is present in the azurophil granules of leukocytes and is known to activate several cells that express PARs. In prostaglandin F2α (3 μM)-precontracted rings from porcine pulmonary arteries with intact endothelium, cathepsin G caused concentration-dependent relaxant responses (pEC50=9.64±0.12). The endothelium-dependent relaxant effect of cathepsin G could also be demonstrated in porcine coronary arteries (pEC50=9.23±0.07). In pulmonary arteries the cathepsin G-induced relaxation was inhibited after blockade of nitric oxide synthesis by L-NAME (200 μM) and was absent in endothelium-denuded vessels. Bradykinin- and cathepsin G-induced relaxant effects were associated with a 5.7 fold and 2.4 fold increase in the concentration of cyclic GMP, respectively. Compared with thrombin and trypsin, which also produced an endothelium-dependent relaxation in pulmonary arteries, cathepsin G was 2.5 and four times more potent, respectively. Cathepsin G caused only small homologous desensitization. In cathepsin G-challenged vessels, thrombin was still able to elicit a relaxant effect. The effects of cathepsin G were blocked by soybean trypsin inhibitor (IC50=0.043 μg ml−1), suggesting that proteolytic activity is essential for induction of relaxation. Recombinant acetyl-eglin C proved to be a potent inhibitor (IC50=0.14 μg ml−1) of the cathepsin G effect, whereas neither indomethacin (3 μM) nor the thrombin inhibitor hirudin (5 ATU ml−1) elicited any inhibitory activity. Due to their polyanionic structure defibrotide (IC50=0.11 μg ml−1), heparin (IC50=0.48 μg ml−1) and suramin (IC50=1.85 μg ml−1) diminished significantly the relaxation in response to the basic protein cathepsin G. In conclusion, like

  10. (1-Butyl-4-methyl-pyridinium)[Cu(SCN)2]: a coordination polymer and ionic liquid.

    Science.gov (United States)

    Spielberg, Eike T; Edengeiser, Eugen; Mallick, Bert; Havenith, Martina; Mudring, Anja-Verena

    2014-04-25

    The compound (C4C1py)[Cu(SCN)2], (C4C1py = 1-Butyl-4-methyl-pyridinium), which can be obtained from CuSCN and the ionic liquid (C4C1py)(SCN), turns out to be a new organic-inorganic hybrid material as it qualifies both, as a coordination polymer and an ionic liquid. It features linked [Cu(SCN)2](-) units, in which the thiocyanates bridge the copper ions in a μ1,3-fashion. The resulting one-dimensional chains run along the a axis, separated by the C4C1py counterions. Powder X-ray diffraction not only confirms the single-crystal X-ray structure solution but proves the reformation of the coordination polymer from an isotropic melt. However, the materials shows a complex thermal behavior often encountered for ionic liquids such as a strong tendency to form a supercooled melt. At a relatively high cooling rate, glass formation is observed. When heating this melt in differential scanning calorimetry (DSC) and temperature-dependent polarizing optical microscopy (POM), investigations reveal the existence of a less thermodynamically stable crystalline polymorph. Raman measurements conducted at 10 and 100 °C point towards the formation of polyanionic chain fragments in the melt. Solid-state UV/Vis spectroscopy shows a broad absorption band around 18,870 cm(-1) (530 nm) and another strong one below 20,000 cm(-1) (<500 nm). The latter is attributed to the d(Cu(I))→π*(SCN)-MLCT (metal-to-ligand charge transfer) transition within the coordination polymer yielding an energy gap of 2.4 eV. At room temperature and upon irradiation with UV light, the material shows a weak fluorescence band at 15,870 cm(-1) (630 nm) with a quantum efficiency of 0.90(2) % and a lifetime of 131(2) ns. Upon lowering the temperature, the luminescence intensity strongly increases. Simultaneously, the band around 450 nm in the excitation spectrum decreases. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Effect of alterations in glomerular charge on deposition of cationic and anionic antibodies to fixed glomerular antigens in the rat.

    Science.gov (United States)

    Adler, S; Baker, P; Pritzl, P; Couser, W G

    1985-07-01

    5 days (controls: 68 +/- 21 mg/day; protamine sulfate-treated: 65 +/- 14 mg/day; n = 25, P greater than 0.08). These results demonstrate that treatment to reduce glomerular polyanion does not significantly alter the ratio of cationic to anionic antibodies to fixed glomerular antigens that deposit in the glomerulus, or reduce proteinuria caused by deposition of antibody to a fixed subepithelial antigen.

  12. Regioselective Sequential Modification of Chitosan via Azide-Alkyne Click Reaction: Synthesis, Characterization, and Antimicrobial Activity of Chitosan Derivatives and Nanoparticles

    Science.gov (United States)

    Sarwar, Atif; Katas, Haliza; Samsudin, Siti Noradila; Zin, Noraziah Mohamad

    2015-01-01

    Recently, the attention of researchers has been drawn toward the synthesis of chitosan derivatives and their nanoparticles with enhanced antimicrobial activities. In this study, chitosan derivatives with different azides and alkyne groups were synthesized using click chemistry, and these were further transformed into nanoparticles by using the ionotropic gelation method. A series of chitosan derivatives was successfully synthesized by regioselective modification of chitosan via an azide-alkyne click reaction. The amino moieties of chitosan were protected during derivatization by pthaloylation and subsequently unblocked at the end to restore their functionality. Nanoparticles of synthesized derivatives were fabricated by ionic gelation to form complexes of polyanionic penta-sodium tripolyphosphate (TPP) and cationic chitosan derivatives. Particle size analysis showed that nanoparticle size ranged from 181.03 ± 12.73 nm to 236.50 ± 14.32 nm and had narrow polydispersity index and positive surface charge. The derivatives and corresponding nanoparticles were evaluated in vitro for antibacterial and antifungal activities against three gram-positive and gram-negative bacteria and three fungal strains, respectively. The minimum inhibitory concentration (MIC) of all derivatives ranged from 31.3 to 250 µg/mL for bacteria and 188 to1500 µg/mL for fungi and was lower than that of native chitosan. The nanoparticles with MIC ranging from 1.56 to 25 µg/mLfor bacteria and 94 to 750 µg/mL for fungi exhibited higher activity than the chitosan derivatives. Chitosan O-(1-methylbenzene) triazolyl carbamate and chitosan O-(1-methyl phenyl sulfide) triazolyl carbamate were the most active against the tested bacterial and fungal strains. The hemolytic assay on erythrocytes and cell viability test on two different cell lines (Chinese hamster lung fibroblast cells V79 and Human hepatic cell line WRL68) demonstrated the safety; suggesting that these derivatives could be used in future

  13. The new Zintl phases Eu{sub 21}Cd{sub 4}Sb{sub 18} and Eu{sub 21}Mn{sub 4}Sb{sub 18}

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Yi; Darone, Gregory M.; Bobev, Svilen, E-mail: bobev@udel.edu

    2016-06-15

    Crystals of two new Zintl compounds, Eu{sub 21}Mn{sub 4}Sb{sub 18} and Eu{sub 21}Cd{sub 4}Sb{sub 18} have been synthesized using the molten metal flux method, and their structures have been established by single-crystal X-ray diffraction. Both compounds are isotypic and crystallize in the monoclinic space group C2/m (No. 12, Z=4). The structures are based on edge- and corner-shared MnSb{sub 4} or CdSb{sub 4} tetrahedra, which make octameric [Mn{sub 8}Sb{sub 22}] or [Cd{sub 8}Sb{sub 22}] polyanions. Homoatomic Sb–Sb bonds are present in both structures. The Eu atoms take the role of Eu{sup 2+}cations with seven unpaired 4f electrons, as suggested by the temperature-dependent magnetization measurements. The magnetic susceptibilities of Eu{sub 21}Mn{sub 4}Sb{sub 18} and Eu{sub 21}Cd{sub 4}Sb{sub 18} indicate that both phases order anti-ferromagnetically with Néel temperatures of ca. 7 K and ca. 10 K, respectively. The unpaired 3d electrons of the Mn atoms in Eu{sub 21}Mn{sub 4}Sb{sub 18} do contribute to the magnetic response, however, the bulk magnetization measurements do not provide evidence for long-range ordering of the Mn spins down to 5 K. Electrical resistivity measurements suggest that both compounds are narrow band gap semiconductors. - Graphical abstract: Eu{sub 21}Mn{sub 4}Sb{sub 18} and Eu{sub 21}Cd{sub 4}Sb{sub 18} have complex monoclinic structures, based on MnSb{sub 4} and CdSb{sub 4} tetrahedra, both edge- and corner-shared. A perspective of the crystal structure is shown, as viewed along the b axis. Display Omitted - Highlights: • Eu{sub 21}Mn{sub 4}Sb{sub 18} and Eu{sub 21}Cd{sub 4}Sb{sub 18} are novel compounds in the respective ternary phase diagrams. • For both structures, the Zintl-Klemm rules are followed, and both are small gap semiconductors. • Eu{sub 21}Mn{sub 4}Sb{sub 18} and Eu{sub 21}Cd{sub 4}Sb{sub 18} are air-stable Zintl phases and could be new thermoelectric materials.

  14. Damaged Neocortical Perineuronal Nets Due to Experimental Focal Cerebral Ischemia in Mice, Rats and Sheep

    Directory of Open Access Journals (Sweden)

    Wolfgang Härtig

    2017-08-01

    Full Text Available As part of the extracellular matrix (ECM, perineuronal nets (PNs are polyanionic, chondroitin sulfate proteoglycan (CSPG-rich coatings of certain neurons, known to be affected in various neural diseases. Although these structures are considered as important parts of the neurovascular unit (NVU, their role during evolution of acute ischemic stroke and subsequent tissue damage is poorly understood and only a few preclinical studies analyzed PNs after acute ischemic stroke. By employing three models of experimental focal cerebral ischemia, this study was focused on histopathological alterations of PNs and concomitant vascular, glial and neuronal changes according to the NVU concept. We analyzed brain tissues obtained 1 day after ischemia onset from: (a mice after filament-based permanent middle cerebral artery occlusion (pMCAO; (b rats subjected to thromboembolic MACO; and (c sheep at 14 days after electrosurgically induced focal cerebral ischemia. Multiple fluorescence labeling was applied to explore simultaneous alterations of NVU and ECM. Serial mouse sections labeled with the net marker Wisteria floribunda agglutinin (WFA displayed largely decomposed and nearly erased PNs in infarcted neocortical areas that were demarcated by up-regulated immunoreactivity for vascular collagen IV (Coll IV. Subsequent semi-quantitative analyses in mice confirmed significantly decreased WFA-staining along the ischemic border zone and a relative decrease in the directly ischemia-affected neocortex. Triple fluorescence labeling throughout the three animal models revealed up-regulated Coll IV and decomposed PNs accompanied by activated astroglia and altered immunoreactivity for parvalbumin, a calcium-binding protein in fast-firing GABAergic neurons which are predominantly surrounded by neocortical PNs. Furthermore, ischemic neocortical areas in rodents simultaneously displayed less intense staining of WFA, aggrecan, the net components neurocan, versican and the

  15. Precise engineering of siRNA delivery vehicles to tumors using polyion complexes and gold nanoparticles.

    Science.gov (United States)

    Kim, Hyun Jin; Takemoto, Hiroyasu; Yi, Yu; Zheng, Meng; Maeda, Yoshinori; Chaya, Hiroyuki; Hayashi, Kotaro; Mi, Peng; Pittella, Frederico; Christie, R James; Toh, Kazuko; Matsumoto, Yu; Nishiyama, Nobuhiro; Miyata, Kanjiro; Kataoka, Kazunori

    2014-09-23

    For systemic delivery of siRNA to solid tumors, a size-regulated and reversibly stabilized nanoarchitecture was constructed by using a 20 kDa siRNA-loaded unimer polyion complex (uPIC) and 20 nm gold nanoparticle (AuNP). The uPIC was selectively prepared by charge-matched polyionic complexation of a poly(ethylene glycol)-b-poly(L-lysine) (PEG-PLL) copolymer bearing ∼40 positive charges (and thiol group at the ω-end) with a single siRNA bearing 40 negative charges. The thiol group at the ω-end of PEG-PLL further enabled successful conjugation of the uPICs onto the single AuNP through coordinate bonding, generating a nanoarchitecture (uPIC-AuNP) with a size of 38 nm and a narrow size distribution. In contrast, mixing thiolated PEG-PLLs and AuNPs produced a large aggregate in the absence of siRNA, suggesting the essential role of the preformed uPIC in the formation of nanoarchitecture. The smart uPIC-AuNPs were stable in serum-containing media and more resistant against heparin-induced counter polyanion exchange, compared to uPICs alone. On the other hand, the treatment of uPIC-AuNPs with an intracellular concentration of glutathione substantially compromised their stability and triggered the release of siRNA, demonstrating the reversible stability of these nanoarchitectures relative to thiol exchange and negatively charged AuNP surface. The uPIC-AuNPs efficiently delivered siRNA into cultured cancer cells, facilitating significant sequence-specific gene silencing without cytotoxicity. Systemically administered uPIC-AuNPs showed appreciably longer blood circulation time compared to controls, i.e., bare AuNPs and uPICs, indicating that the conjugation of uPICs onto AuNP was crucial for enhancing blood circulation time. Finally, the uPIC-AuNPs efficiently accumulated in a subcutaneously inoculated luciferase-expressing cervical cancer (HeLa-Luc) model and achieved significant luciferase gene silencing in the tumor tissue. These results demonstrate the strong

  16. Patterns in groundwater chemistry resulting from groundwater flow

    Science.gov (United States)

    Stuyfzand, Pieter J.

    qualité de l'eau vers une absence de fluctuations, de polluées vers non polluées, d'acides vers basiques, d'oxygénées vers anoxiques et méthanogènes, depuis des échanges de base inexistants vers des échanges significatifs, de l'eau douce vers l'eau saumâtre. Ceci est montré pour une nappe d'eau douce dans une dune côtière des Pays-Bas. Dans "l'hydrosome", on montre que la disparition du carbonate de calcium par lessivage à plus de 15m et celle de cations adsorbés d'origine marine (Na+, K+ et Mg2+) à plus de 2500m vers l'aval-gradient correspond à environ 5000 ans d'écoulement, depuis que la barrière de la plage avec les dunes s'est mise en place. Les zones d'alimentation ponctuelle dans les dunes sont mises en évidence par l'eau souterraine montrant une plus faible évolution prograde de sa qualité que l'eau souterraine de la dune alentour. L'eau du Rhin utilisée pour la réalimentation artificielle dans les dunes a fourni des types hydrochimiques distincts, qui marquent l'écoulement, le mélange et les âges de l'eau souterraine. Resumen El flujo subterráneo tiene una gran importancia sobre la hidroquímica de un sistema ya que reduce la mezcla por difusión, transporta las huellas químicas y biológicas de las acciones antrópicas en la zona de recarga y drena el sistema acuífero. Las tendencias globales vienen regidas por las diferencias en el flujo de agua meteórica que atraviesa el subsuelo. En un hidrosoma individual (cuerpo de agua de un origen específico), se suele desarrollar la siguiente línea de evolución (secuencia de facies) en la dirección del flujo: de gran a nula fluctuación en la calidad del agua, de agua contaminada a no contaminada, de ácida a básica, de óxica a anóxica-metanogénica, de nulo a importante cambio de base y de agua dulce a salobre. Esto puede verse, por ejemplo, en las aguas dulces presentes en las dunas costeras de Holanda. En este hidrosoma, el lixiviado de carbonato cálcico, hasta 15m, y de

  17. A frogspawn-inspired hierarchical porous NaTi2(PO4)3-C array for high-rate and long-life aqueous rechargeable sodium batteries

    Science.gov (United States)

    Zhao, Baidan; Lin, Bo; Zhang, Sen; Deng, Chao

    2015-11-01

    Hollow micro/nano-arrays have attracted tremendous attention in the field of energy conversion and storage, but such structures usually compromise the volumetric energy density of the electrode materials. Frogspawn consists of a spawn core and a transparent jelly shell organized in a hierarchical porous array, which exhibits superior mechanical strength and high-efficiency oxygen permeability. It can be used as a model for designing a new high-performance electrode material, which has advantages such as a high surface area, fast mass transport and superior durability. Herein, we report a frogspawn-like NaTi2(PO4)3/C array prepared by a facile preform impregnation strategy. The framework is formed by a hollow carbon sphere connected by the NaTi2(PO4)3/C skeleton, and its hollow is filled with the NaTi2(PO4)3 nanospheres. The whole hierarchical porous three-dimensional array copies the structure of a frogspawn. This unique structure not only enables easy electrolyte percolation and fast electron/ion transport, but also enhances the reversible capacity and cycling durability. When it is applied as an anode of the aqueous sodium ion battery, it exhibits favorable high rate capability and superior cycling stability, and retains 89% of the initial capacity after two thousand cycles at 20 C. Moreover, the full cell using the frogspawn-inspired NaTi2(PO4)3-C as the anode and Na0.44MnO2 as the cathode is capable of ultralong cycling up to one thousand cycles at alternate 10 and 60 C, which is among the best of state-of-the-art aqueous sodium ion systems. Therefore, the frogspawn-inspired architecture provides a new strategy to the tailored design of polyanion materials for high-power applications.Hollow micro/nano-arrays have attracted tremendous attention in the field of energy conversion and storage, but such structures usually compromise the volumetric energy density of the electrode materials. Frogspawn consists of a spawn core and a transparent jelly shell organized in

  18. Synthesis of gels with basis of titanium tungstates as matrixes of radioactive generators; Sintesis de geles a base de titanio tungstenatos como matrices de generadores radiactivos

    Energy Technology Data Exchange (ETDEWEB)

    Galico C, L

    2005-07-01

    The heteropolyanions, compounds formed by the union of molybdates or tungstates polyanions with atoms of metals like zirconium, titanium, cerium, thorium, tin, etc., have been used as generator matrixes of {sup 99m} Tc or {sup 188} Re. Particularly they have been studied and produced successfully in our laboratory, generators of {sup 99} Mo/ {sup 99}m Tc at basis of gels zirconium molybdates and titanium molybdates. Considering that the molybdenum and tungsten, as well as the technetium and the rhenium, its belong to the same groups of transition metals, it is feasible that gels can be synthesized at basis of titanium tungstates, continuing a methodology similar to that of the gels titanium molybdates or zirconium molybdates, to produce generators {sup 188} W/ {sup 188} Re. The {sup 188} Re possess nuclear characteristics that make it attractive for therapeutic applications, since, it emits {beta}{sup -} particles of a great energy (2.12 MeV); joined to the possibility of being able to unite to different ligands (bifunctional agents) and biomolecules (antibodies or fragments of proteins), as it makes the {sup 99m} Tc, useful in radioimmunotherapy. Commercially the {sup 188} Re generators use a chromatographic column loaded with alumina where the {sup 188} Re, it is adsorbed and eluted the {sup 188} ReO{sub 4}{sup -} by means of a saline solution The alumina adsorbs around 0.2% of the {sup 188} Re, situation that forces to use {sup 188} Re of a high specific activity. The use of the gels technology, allows to work with medium or low specific activities of {sup 188} Re, opening the possibility of their production in countries whose nuclear capacity is medium or low. In particular, the synthesized gels with basis of titanium offer the possibility of being synthesized with non active material, for later on to be irradiated and directly produce the generator, since, the titanium {sup 51} Ti, unique radioisotope produced by the titanium, has a half life of 5.79 min. This

  19. Syntheses, and crystal and electronic structures of the new Zintl phases Na2ACdSb2 and K2ACdSb2 (A=Ca, Sr, Ba, Eu, Yb): Structural relationship with Yb2CdSb2 and the solid solutions Sr2-xAxCdSb2, Ba2-xAxCdSb2 and Eu2-xYbxCdSb2

    International Nuclear Information System (INIS)

    Saparov, Bayrammurad; Saito, Maia; Bobev, Svilen

    2011-01-01

    Presented are the details of the syntheses, crystal and electronic structures of a new family of Zintl phases Na 2 ACdSb 2 and K 2 ACdSb 2 (A=Ca, Sr, Ba, Eu, Yb), as well as the solid solutions Sr 2-x A x CdSb 2 , Ba 2-x A x CdSb 2 and Eu 2-x Yb x CdSb 2 . The structures of Na 2 ACdSb 2 and K 2 ACdSb 2 (A=Ca, Sr, Ba, Eu, Yb) were determined to be of a new type with the non-centrosymmetric space group Pmc2 1 (no. 26), Pearson symbol oP12, with lattice parameters a=4.684(1)-4.788(1) A; b=9.099(3)-9.117(2) A; c=7.837(1)-8.057(2) A for the Na 2 ACdSb 2 series, and a=4.6637(9)-5.0368(8) A; b=9.100(2)-9.8183(15) A; and c=7.7954(15)-8.4924(13) A for K 2 ACdSb 2 , respectively. The solid solutions Sr 2-x A x CdSb 2 , Ba 2-x A x CdSb 2 and Eu 2-x Yb x CdSb 2 (x∼1) are isostructural and isoelectronic to the recently reported Yb 2 CdSb 2 (space group Cmc2 1 (no. 36), Pearson symbol cP20). All discussed structures are based upon CdSb 2 4- polyanionic layers, similar to the ones observed in Yb 2 CdSb 2 , with various alkali- and/or alkaline-earth cations coordinated to them. Magnetic susceptibility and Seebeck coefficient measurements on selected Eu 2-x Yb x CdSb 2 samples, taken at low temperatures up to 300 K, are also reported. -- Graphical abstract: The quaternary Zintl phases Na 2 ACdSb 2 and K 2 ACdSb 2 (A=Ca, Sr, Ba, Eu, Yb) with novel layered structures have been synthesized for the first time and structurally characterized by single-crystal X-ray diffraction. Reported as well are the results from crystallographic and property studies of the closely related solid solutions Sr 2-x A x CdSb 2 , Ba 2-x A x CdSb 2 (x∼1), and Eu 2-x Yb x CdSb 2 (1 2 ACdSb 2 and K 2 ACdSb 2 (A=Ca, Sr, Ba, Eu, Yb) are new quaternary Zintl phases. → Sr 2-x A x CdSb 2 , Ba 2-x A x CdSb 2 (x∼1), and Eu 2-x Yb x CdSb 2 (1 4 tetrahedra. → Eu 2-x Yb x CdSb 2 (1< x<2) exhibit high Seebeck coefficient (217 μV/K at RT).

  20. Effect of cyanato, azido, carboxylato, and carbonato ligands on the formation of cobalt(II) polyoxometalates: characterization, magnetic, and electrochemical studies of multinuclear cobalt clusters.

    Science.gov (United States)

    Lisnard, Laurent; Mialane, Pierre; Dolbecq, Anne; Marrot, Jérôme; Clemente-Juan, Juan Modesto; Coronado, Eugenio; Keita, Bineta; de Oliveira, Pedro; Nadjo, Louis; Sécheresse, Francis

    2007-01-01

    Five Co(II) silicotungstate complexes are reported. The centrosymmetric heptanuclear compound K(20)[{(B-beta-SiW(9)O(33)(OH))(beta-SiW(8)O(29)(OH)(2))Co(3)(H(2)O)}(2)Co(H(2)O)(2)]47 H(2)O (1) consists of two {(B-beta-SiW(9)O(33)(OH))(beta-SiW(8)O(29)(OH)(2))Co(3)(H(2)O)} units connected by a {CoO(4)(H(2)O)(2)} group. In the chiral species K(7)[Co(1.5)(H(2)O)(7))][(gamma-SiW(10)O(36))(beta-SiW(8)O(30)(OH))Co(4)(OH)(H(2)O)(7)]36 H(2)O (2), a {gamma-SiW(10)O(36)} and a {beta-SiW(8)O(30)(OH)} unit enclose a mononuclear {CoO(4)(H(2)O)(2)} group and a {Co(3)O(7)(OH)(H(2)O)(5)} fragment. The two trinuclear Co(II) clusters present in 1 enclose a mu(4)-O atom, while in 2 a mu(3)-OH bridging group connects the three paramagnetic centers of the trinuclear unit, inducing significantly larger Co-L-Co (L=mu(4)-O (1), mu(3)-OH (2)) bridging angles in 2 (theta(av(Co-L-Co))=99.1 degrees ) than in 1 (theta(av(Co-L-Co))=92.8 degrees ). Weaker ferromagnetic interactions were found in 2 than in 1, in agreement with larger Co-L-Co angles in 2. The electrochemistry of 1 was studied in detail. The two chemically reversible redox couples observed in the positive potential domain were attributed to the redox processes of Co(II) centers, and indicated that two types of Co(II) centers in the structure were oxidized in separate waves. Redox activity of the seventh Co(II) center was not detected. Preliminary experiments indicated that 1 catalyzes the reduction of nitrite and NO. Remarkably, a reversible interaction exists with NO or related species. The hybrid tetranuclear complexes K(5)Na(3)[(A-alpha-SiW(9)O(34))Co(4)(OH)(3)(CH(3)COO)(3)]18 H(2)O (3) and K(5)Na(3)[(A-alpha-SiW(9)O(34))Co(4)(OH)(N(3))(2)(CH(3)COO)(3)]18 H(2)O (4) were characterized: in both, a tetrahedral {Co(4)(L(1))(L(2))(2)(CH(3)COO)(3)} (3: L(1)=L(2)=OH; 4: L(1)=OH, L(2)=N(3)) unit capped the [A-alpha-SiW(9)O(34)](10-) trivacant polyanion. The octanuclear complex K(8)Na(8)[(A-alpha-SiW(9)O(34))(2)Co(8)(OH)(6)(H(2)O)(2)(CO(3

  1. Synthesis of gels with basis of titanium tungstates as matrixes of radioactive generators

    International Nuclear Information System (INIS)

    Galico C, L.

    2005-01-01

    The heteropolyanions, compounds formed by the union of molybdates or tungstates polyanions with atoms of metals like zirconium, titanium, cerium, thorium, tin, etc., have been used as generator matrixes of 99m Tc or 188 Re. Particularly they have been studied and produced successfully in our laboratory, generators of 99 Mo/ 99 m Tc at basis of gels zirconium molybdates and titanium molybdates. Considering that the molybdenum and tungsten, as well as the technetium and the rhenium, its belong to the same groups of transition metals, it is feasible that gels can be synthesized at basis of titanium tungstates, continuing a methodology similar to that of the gels titanium molybdates or zirconium molybdates, to produce generators 188 W/ 188 Re. The 188 Re possess nuclear characteristics that make it attractive for therapeutic applications, since, it emits β - particles of a great energy (2.12 MeV); joined to the possibility of being able to unite to different ligands (bifunctional agents) and biomolecules (antibodies or fragments of proteins), as it makes the 99m Tc, useful in radioimmunotherapy. Commercially the 188 Re generators use a chromatographic column loaded with alumina where the 188 Re, it is adsorbed and eluted the 188 ReO 4 - by means of a saline solution The alumina adsorbs around 0.2% of the 188 Re, situation that forces to use 188 Re of a high specific activity. The use of the gels technology, allows to work with medium or low specific activities of 188 Re, opening the possibility of their production in countries whose nuclear capacity is medium or low. In particular, the synthesized gels with basis of titanium offer the possibility of being synthesized with non active material, for later on to be irradiated and directly produce the generator, since, the titanium 51 Ti, unique radioisotope produced by the titanium, has a half life of 5.79 min. This synthesis method avoids the manipulation of radioactive material during the synthesis of the gels, process

  2. The Zintl Chemistry of the Heavy Tetrel Elements

    Energy Technology Data Exchange (ETDEWEB)

    Klem, Michael Thomas [Iowa State Univ., Ames, IA (United States)

    2002-12-31

    Exploration of the alkali metal/alkaline-earth metal/heavy tetrel (Sn or Pb) systems has revealed a vast array of new chemistry and novel structure types. The structures and properties of these new materials have been studied in an attempt to understand the chemistry of these and other related systems. The first phase reported is Rb4Pb9 (K4Pb9 type). The compound contains two different types of Pb94- deltahedra, a monocapped square pyramid and a distorted tricapped trigonal prism. Both cluster geometries correspond to a nido assignment even though the tricapped trigonal prism is not the classic Wade's rules nido deltahedron expected for a monocapped square antiprism. Also, a series of compounds that contain square pyramidal Tt5 polyanions of tin and lead has been obtained in alkaline-earth or rare-earth metal-tetrel systems by direct fusion of the elements to yield Sr3Sn5, Ba3Pb5, and La3Sn5. These phases contain square pyramidal clusters of the tetrel elements that are weakly interlinked into chains via two types of longer intercluster interactions that are mediated by bridging cations and substantially influenced by cation size and the free electron count. Attempts at incorporating another main-group element to form heteroatomic clusters were also successful. In the case of A5InPb8 (A = K, Rb), the compounds contain clusters composed of two Pb4 tetrahedra that are interbridged by a lone μ6-In atom. The InPb8 units are weakly interlinked into sheets in the ab plane by long intercluster Pb-Pb interactions. Using As led to the formation of the compound K5As3Pb3 which is made up of As3Pb35- crown clusters that can be likened to a 6-atom hypho-cluster based on the tricapped trigonal parent as the closo

  3. The new barium zinc mercurides Ba3ZnHg10 and BaZn0.6Hg3.4 – Synthesis, crystal and electronic structure

    International Nuclear Information System (INIS)

    Schwarz, Michael; Wendorff, Marco; Röhr, Caroline

    2012-01-01

    The title compounds Ba 3 ZnHg 10 and BaZn 0.6 Hg 3.4 were synthesized from stoichiometric ratios of the elements in Ta crucibles. Their crystal structures, which both represent new structure types, have been determined using single crystal X-ray data. The structure of Ba 3 ZnHg 10 (orthorhombic, oP28, space group Pmmn, a=701.2(3), b=1706.9(8), c=627.3(3)pm, Z=2, R1=0.0657) contains folded 4 4 Hg nets, where the meshes form the bases of flat rectangular pyramids resembling the structure of BaAl 4 . The flat pyramids are connected via Hg–Zn/Hg bonds, leaving large channels at the folds, in which Ba(1) and Hg(2) atoms alternate. Whereas the remaining Hg/Zn atoms form a covalent 3D network of three- to five-bonded atoms with short M–M distances (273–301 pm; CN 9–11), the Hg(2) atoms in the channels adopt a comparatively large coordination number of 12 and increased distances (317–348 pm) to their Zn/Hg neighbours. In the structure of BaZn 0.6 Hg 3.4 (cubic, cI320, space group I4 ¯ 3d, a=2025.50(7) pm, Z=64, R1=0.0440), with a chemical composition not much different from that of Ba 3 ZnHg 10 , the Zn/Hg atoms of the mixed positions M(1/2) are arranged in an slightly distorted primitive cubic lattice with a 4×4×4 subcell relation to the unit cell. The 24 of the originating 64 cubes contain planar cis tetramers Hg(5,6) 4 with Hg in a nearly trigonal planar or tetrahedral coordination. In another 24 of the small cubes, two opposing faces are decorated by Hg(3,4) 2 dumbbells, two by Ba(2) atoms respectively. The third type of small cubes are centered by Ba(1) atoms only. The complex 3D polyanionic Hg/Zn network thus formed is compared with the Hg partial structure in Rb 3 Hg 20 applying a group-subgroup relation. Despite their different overall structures, the connectivity of the negatively charged Hg atoms, the rather metallic Zn bonding characteristic (as obtained from FP-LAPW band structure calculations) and the coordination number of 16 for all Ba cations

  4. Terminal Gold-Oxo Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Cao, R.; Anderson, T.M.; Piccoli, P.M.B.; Schultz, A.J.; Koetzle, T.F.; Geletii, Y.V.; Slonkina, E.; Hedman, B.; Hodgson, K.O.; Hardcastle, K.I.; Fang, X.; Kirk, M.L.; Knottenbelt, S.; Kogerler, P.; Musaev, D.G.; Morokuma, K.; Takahashi, M.; Hill, C.L.; /Emory U. /Argonne /SLAC, SSRL /New Mexico U. /Iowa State U. /Toho U.

    2007-10-19

    In contradiction to current bonding paradigms, two terminal Au-oxo molecular complexes have been synthesized by reaction of AuCl{sub 3} with metal oxide-cluster ligands that model redox-active metal oxide surfaces. Use of K{sub 10}[{alpha}{sub 2}-P{sub 2}W{sub 17}O{sub 61}] x 20H{sub 2}O and K{sub 2}WO{sub 4} (forming the [A-PW{sub 9}O{sub 34}]{sup 9-} ligand in situ) produces K{sub 15}H{sub 2}[Au(O)(OH{sub 2})P{sub 2}W{sub 18}O{sub 68}] x 25H{sub 2}O (1); use of K{sub 10}[P{sub 2}W{sub 20}O{sub 70}(OH{sub 2}){sub 2}] x 22H{sub 2}O (3) produces K{sub 7}H{sub 2}[Au(O)(OH{sub 2})P{sub 2}W{sub 20}O{sub 70}(OH{sub 2}){sub 2}] x 27H{sub 2}O (2). Complex 1 crystallizes in orthorhombic Fddd, with a = 28.594(4) Angstroms, b = 31.866(4) Angstroms, c = 38.241(5) Angstroms, V = 34844(7) Angstroms{sup 3}, Z = 16 (final R = 0.0540), and complex 2 crystallizes in hexagonal P6(3)/mmc, with a = 16.1730(9) Angstroms, b = 16.1730(9) Angstroms, c = 19.7659(15) Angstroms, V = 4477.4(5) Angstroms{sup 3}, Z = 2 (final R = 0.0634). The polyanion unit in 1 is disorder-free. Very short ({approx}1.76 Angstroms) Au-oxo distances are established by both X-ray and 30 K neutron diffraction studies, and the latter confirms oxo and trans aqua (H2O) ligands on Au. Seven findings clarify that Au and not W is present in the Au-oxo position in 1 and 2. Five lines of evidence are consistent with the presence of d8 Au(III) centers that are stabilized by the flanking polytungstate ligands in both 1 and 2: redox titrations, electrochemical measurements, 17 K optical spectra, Au L2 edge X-ray absorption spectroscopy, and Au-oxo bond distances. Variable-temperature magnetic susceptibility data for crystalline 1 and 2 establish that both solids are diamagnetic, and {sup 31}P and {sup 17}O NMR spectroscopy confirm that both remain diamagnetic in solution. Both complexes have been further characterized by FT-IR, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and other techniques.

  5. Hexavalent chromium removal by chitosan modified-bioreduced nontronite

    Science.gov (United States)

    Singh, Rajesh; Dong, Hailiang; Zeng, Qiang; Zhang, Li; Rengasamy, Karthikeyan

    2017-08-01

    Recent efforts have focused on structural Fe(II) in chemically or biologically reduced clay minerals to immobilize Cr(VI) from aqueous solution, but the coulombic repulsion between the negatively charged clay surface and the polyanionic form of Cr(VI), e.g., dichromate, can hinder the effectiveness of this process. The purpose of this study was to investigate the efficiency and mechanism of Cr(VI) removal by a charge-reversed nontronite (NAu-2), an Fe-rich smectite. Chitosan, a linear polysaccharide derived from chitin found in soil and groundwater, was used to reverse the charge of NAu-2. Intercalation of chitosan into NAu-2 interlayer increased the basal d-spacing of NAu-2 from 1.23 nm to 1.83 nm and zeta potential from -27.17 to +34.13 mV, with the amount of increase depending on chitosan/NAu-2 ratio. Structural Fe(III) in chitosan-exchanged NAu-2 was then biologically reduced by an iron-reducing bacterium Shewanella putrefaciens CN32 in bicarbonate buffer with lactate as the sole electron donor, with and without electron shuttle, AQDS. Without AQDS, the extent of Fe(III) reduction increased from the lowest (∼9%) for the chitosan-free NAu-2 to the highest (∼12%) for the highest chitosan loaded NAu-2 (3:1 ratio). This enhancement of Fe(III) reduction was likely due to the attachment of negatively charged bacterial cells to charge-reversed (e.g., positively charged) NAu-2 surfaces, facilitating the electron transfer between cells and structural Fe(III). With AQDS, Fe(III) reduction extent doubled relative to those without AQDS, but the enhancement effect was similar across all chitosan loadings, suggesting that AQDS was more important than chitosan in enhancing Fe(III) bioreduction. Chitosan-exchanged, biologically reduced NAu-2 was then utilized for removing Cr(VI) in batch experiments with three consecutive spikes of 50 μM Cr. With the first Cr spike, the rate of Cr(VI) removal by charged-reversed NAu-2 that was bioreduced without and with AQDS was ∼1

  6. Synthesis, structure and chemical bonding of CaFe{sub 2−x}Rh{sub x}Si{sub 2} (x=0, 1.32, and 2) and SrCo{sub 2}Si{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Hlukhyy, Viktor, E-mail: viktor.hlukhyy@lrz.tu-muenchen.de; Hoffmann, Andrea V.; Fässler, Thomas F.

    2013-07-15

    The finding of superconductivity in Ba{sub 0.6}K{sub 0.4}Fe{sub 2}As{sub 2} put the attention on the investigation of compounds that crystallize with ThCr{sub 2}Si{sub 2} structure type such as AT{sub 2}X{sub 2} (A=alkali/alkaline earth/rare earth element; T=transition metal and X=element of the 13–15th group). In this context the silicides CaFe{sub 2}Si{sub 2}, CaFe{sub 0.68(6)}Rh{sub 1.32(6)}Si{sub 2}, CaRh{sub 2}Si{sub 2} and SrCo{sub 2}Si{sub 2} have been synthesized by reaction of the elements under an argon atmosphere. Single crystals were obtained by special heat treatment in welded niobium/tantalum ampoules. The compounds were investigated by means of powder and single crystal X-ray diffraction. All compounds crystallize in the ThCr{sub 2}Si{sub 2}-type structure with space group I4/mmm (No. 139): a=3.939(1) Å, c=10.185(1) Å, R{sub 1}=0.045, 85 F{sup 2} values, 8 variable parameters for CaFe{sub 2}Si{sub 2}; a=4.0590(2) Å, c=9.9390(8) Å, R{sub 1}=0.030, 90 F{sup 2} values, 10 variable parameters for CaFe{sub 0.68(6)}Rh{sub 1.32(6)}Si{sub 2}; a=4.0695(1) Å, c=9.9841(3) Å, R{sub 1}=0.031, 114 F{sup 2} values, 9 variable parameters for CaRh{sub 2}Si{sub 2}; and a=3.974(1) Å, c=10.395(1) Å, R{sub 1}=0.036, 95 F{sup 2} values, 8 variable parameters for SrCo{sub 2}Si{sub 2}. The structure of SrCo{sub 2}Si{sub 2} contains isolated [Co{sub 2}Si{sub 2}]{sup 2−} 2D-layers in the ab-plane whereas in CaFe{sub 2−x}Rh{sub x}Si{sub 2} the [T{sub 2}Si{sub 2}] layers (T=Fe and Rh) are interconnected along the c-axis via Si3Si bonds resulting in a three-dimentional (3D) [T{sub 2}Si{sub 2}]{sup 2−} polyanions and therefore belong to the so-called collapsed form of the ThCr{sub 2}Si{sub 2}-type structure. The SrCo{sub 2}Si{sub 2} and CaRh{sub 2}Si{sub 2} are isoelectronic to the parent 122 iron–pnictide superconductors AeFe{sub 2}As{sub 2} (Ae=alkaline earth elements), whereas CaFe{sub 2}Si{sub 2} is a full substituted variant (As/Si) of CaFe{sub 2}As{sub 2

  7. Synthesis, structure and chemical bonding of CaFe2−xRhxSi2 (x=0, 1.32, and 2) and SrCo2Si2

    International Nuclear Information System (INIS)

    Hlukhyy, Viktor; Hoffmann, Andrea V.; Fässler, Thomas F.

    2013-01-01

    The finding of superconductivity in Ba 0.6 K 0.4 Fe 2 As 2 put the attention on the investigation of compounds that crystallize with ThCr 2 Si 2 structure type such as AT 2 X 2 (A=alkali/alkaline earth/rare earth element; T=transition metal and X=element of the 13–15th group). In this context the silicides CaFe 2 Si 2 , CaFe 0.68(6) Rh 1.32(6) Si 2 , CaRh 2 Si 2 and SrCo 2 Si 2 have been synthesized by reaction of the elements under an argon atmosphere. Single crystals were obtained by special heat treatment in welded niobium/tantalum ampoules. The compounds were investigated by means of powder and single crystal X-ray diffraction. All compounds crystallize in the ThCr 2 Si 2 -type structure with space group I4/mmm (No. 139): a=3.939(1) Å, c=10.185(1) Å, R 1 =0.045, 85 F 2 values, 8 variable parameters for CaFe 2 Si 2 ; a=4.0590(2) Å, c=9.9390(8) Å, R 1 =0.030, 90 F 2 values, 10 variable parameters for CaFe 0.68(6) Rh 1.32(6) Si 2 ; a=4.0695(1) Å, c=9.9841(3) Å, R 1 =0.031, 114 F 2 values, 9 variable parameters for CaRh 2 Si 2 ; and a=3.974(1) Å, c=10.395(1) Å, R 1 =0.036, 95 F 2 values, 8 variable parameters for SrCo 2 Si 2 . The structure of SrCo 2 Si 2 contains isolated [Co 2 Si 2 ] 2− 2D-layers in the ab-plane whereas in CaFe 2−x Rh x Si 2 the [T 2 Si 2 ] layers (T=Fe and Rh) are interconnected along the c-axis via Si3Si bonds resulting in a three-dimentional (3D) [T 2 Si 2 ] 2− polyanions and therefore belong to the so-called collapsed form of the ThCr 2 Si 2 -type structure. The SrCo 2 Si 2 and CaRh 2 Si 2 are isoelectronic to the parent 122 iron–pnictide superconductors AeFe 2 As 2 (Ae=alkaline earth elements), whereas CaFe 2 Si 2 is a full substituted variant (As/Si) of CaFe 2 As 2 . The crystal chemistry and chemical bonding in the title compounds are discussed in terms of LMTO band structure calculations and a topological analysis using the Electron Localization Function (ELF). - Graphical abstract: The SrCo 2 Si 2 and CaFe 2−x Rh x Si

  8. Principles of water oxidation and O2-based hydrocarbon transformation by multinuclear catalytic sites

    Energy Technology Data Exchange (ETDEWEB)

    Musaev, Djamaladdin G [Chemistry, Emory University; Hill, Craig L [Chemistry, Emory University; Morokuma, Keiji [Chemistry, Emory University

    2014-10-28

    centers in the active site form another part of considerable interest of our grant because species with such sites [including methane monooxygenase (MMO) and more] are some of the most effective oxygenase catalysts known. Our team conducted the following research on γ-M2-Keggin complexes: (a) investigated stability of the trimer [{Fe3(OH)3(H2O)2}3(γ-SiW10O36)3]15-, 4, in water, and developed the chemistry and catalysis of the di-iron centered POM, [γ(1,2)-SiW10{Fe(OH)}2O38]6-, 5, in organic solvents (Figure 2). We also study the thermodynamic and structural stability of γ-M2-Keggin in aqueous media for different M’s (d-electron metals). We have defined two structural classes of POMs with proximally bound d-electron metal centers. We refer to these structural isomers of the {γ-M2SiW10} family of POMs as “in-pocket” and “out-of pocket”. We have elucidated the factors controlling the structure and stability of the V, Fe, Ru, Tc, Mo and Rh derivatives of [(SiO4)M2(OH)2W10O32]4- using a range of computational tools. We have: (a) demonstrated that heteroatom X in these polyanions may function as an “internal switch” for defining the ground electronic states and, consequently, the reactivity of the γ-M2-Keggin POM complexes; (b) elucidated reactivity of divacant lacunary species and polyperoxotungstates (PPTs), {Xn+O4[WO(O2)2]4}n-, which could be degradation products of γ-M2-Keggin complexes in aqueous media; (c) elucidated the role of the POM ligand in stabilization of {Ru2} and {(Ru-oxo)2} fragments in the reactant and product of the reaction of {γ-[(Xn+O4)Ru2(OH)2W10O32]}(8-n)- (where X = Si4+, P5+ and S6+) with O2, and (d) the mechanisms of olefin epoxidation catalyzed by these di-d-transition metal substituted and divacant lacunary γ-M2-Keggin complexes. III. Complementing the efforts presented above was the development of less time-consuming but reasonably accurate computational methods allowing one to explore more deeply large catalytic systems. We

  9. Mineralogical and geochemical studies on borate deposits from the Shahr- e - Babak playa (Khatoonabad and Robat - Marvast, Kerman province - Iran

    Directory of Open Access Journals (Sweden)

    Atefeh Ghaedi

    2017-11-01

    . and Clark, J.R., 1978. Ulexite, NaCaB5O6 (OH6 . 5H2O: structure refinement, polyanion configuration, hydrogen bonding, and fiber optics. American Mineralogist, 63(12: 160–171. Levy, H.A. and Lisensky, G.C., 1978 .Crystal structures of sodium sulfate decahydrate (Glauber's salt and sodium tetraborate decahydrate (borax. Redetermination by neutron diffraction. Acta Crystallographica, 34(12: 3502-3510. Palache, C., Berman, H. and Frondel, C., 1952. Dana's System of Mineralogy. Geologiska Föreningen i Stockholm Förhandlingar, 74(2: 218-219.‏

  10. FOREWORD: Some thoughts about Jürgen Hafner's work in computational materials science Some thoughts about Jürgen Hafner's work in computational materials science

    Science.gov (United States)

    Heine, Volker

    2011-10-01

    and Kresse G 1994 Structral and electronic properties of clean and hydrogenated diamond (100) surfaces Europhys. Lett. 28 659-64 [10] Krajčí and Hafner J 2008 Ab-initio studies of quasicrystalline surfaces Quasicrystals (Handbook of Metal Physics vol 2) ed T Fujiwara and Y Ishii (Amsterdam: Elsevier) chapter 9, pp 313-55 [11] Raybaud P, Hafner J, Kresse G, Kasztelan S and Toulhoat H 2000 Structure, energetics and electronic properties of the surface of a promoted MoS2 catalyst: an ab-initio local-density-functional study J. Catalysis 190 128-43 [12] Hafner J, Benco L and Bucko T 2006 Acid-based catalysis in zeolites investigated by density-functional methods Top. Catalysis 37 41-54 [13] Hafner J 1989 Formation of polyanionic clusters in liquid potassium-lead alloys: a molecular-dynamics study J. Phys.: Condens. Matter 1 1133-40 [14] Meeks P E 1976 Vibrational spectra and topological structure of tetrahedrally bonded amorphous semiconductors Phil. Mag. 33 897-908 [15] See articles by Heine V, Bullet D, Haydock R and Kelly M J 1980 Solid State Physics—Advances in Research and Applications vol 35, ed H Ehrenreich, D Turnbull and F Seitz (New York: Academic) [16] Hafner J 1980 The dynamical properties of metallic glasses Liquids and Amorphous Metals (NATO-ASI Ser. E vol 36) ed E Lüscher and H Coufal (Sijthoff and Nordhoff: Alpen van Rijn) pp 199-209 [17] Hafner J 1987 From Hamiltonians to Phase Diagrams—The Electronic and Statistical-Mechanical Theory of sp-Bonded Metals and Alloys (Solid State Sciences Series vol 70) (Berlin: Springer) p 415 [18] Hafner J and Heine V 1983 The crystal structure of the elements: pseudopotential theory revisited J. Phys. F: Met. Phys. 13 2479-501 [19] Hafner J and Kahl G 1984 The structure of the elements in the liquid state J. Phys. F: Met. Phys. 14 2259-78 [20] Denton A R and Hafner J 1997 Thermodynamically stable one-component quasicrystals: a density-functional survey of relative stabilities Phys. Rev. B 56 2469-82 [21] Hafner J