One-step synthesis of mesoporous pentasil zeolite with single-unit-cell lamellar structural features

DOEpatents

Tsapstsis, Michael; Zhang, Xueyi

2015-11-17

A method for making a pentasil zeolite material includes forming an aqueous solution that includes a structure directing agent and a silica precursor; and heating the solution at a sufficient temperature and for sufficient time to form a pentasil zeolite material from the silica precursor, wherein the structure directing agent includes a quaternary phosphonium ion.

Anticancer Agents: Does a Phosphonium Behave Like a Gold(I) Phosphine Complex? Let a "Smart" Probe Answer!

PubMed

Ali, Moussa; Dondaine, Lucile; Adolle, Anais; Sampaio, Carla; Chotard, Florian; Richard, Philippe; Denat, Franck; Bettaieb, Ali; Le Gendre, Pierre; Laurens, Véronique; Goze, Christine; Paul, Catherine; Bodio, Ewen

2015-06-11

Gold phosphine complexes, such as auranofin, have been recognized for decades as antirheumatic agents. Clinical trials are now underway to validate their use in anticancer or anti-HIV treatments. However, their mechanisms of action remain unclear. A challenging question is whether the gold phosphine complex is a prodrug that is administered in an inactive precursor form or rather that the gold atom remains attached to the phosphine ligand during treatment. In this study, we present two novel gold complexes, which we compared to auranofin and to their phosphonium analogue. The chosen ligand is a phosphine-based smart probe, whose strong fluorescence depends on the presence of the gold atom. The in vitro biological action of the gold complexes and the phosphonium derivative were investigated, and a preliminary in vivo study in healthy zebrafish larvae allowed us to evaluate gold complex biodistribution and toxicity. The different analyses carried out showed that these gold complexes were stable and behaved differently from phosphonium and auranofin, both in vitro and in vivo. Two-photon microscopy experiments demonstrated that the cellular targets of these gold complexes are not the same as those of the phosphonium analogue. Moreover, despite similar IC50 values in some cancer cell lines, gold complexes displayed a low toxicity in vivo, in contrast to the phosphonium salt. They are therefore suitable for future in vivo investigations.

Phosphoniums as catalysts for metal-free polymerization: Synthesis of well-defined poly(propylene oxide)

NASA Astrophysics Data System (ADS)

Zhang, Jie; Liu, Quan; Ren, Haojun; Zhang, Nanjie; Li, Pengfei; Yang, Kang

2017-11-01

The anionic ring-opening polymerization of propylene oxide (PO) was initiated with glycerol and catalyzed by three new synthetic phosphonium salts, tetrakis (pyrrolidino) phosphonium (Py4P1+), tetrakis (piperidino) phosphonium (Pi4P1+), tetrakis (morpholino) phosphonium (Mo4P1+), and the known tetrakis [cyclohexyl (methyl) amino] phosphonium (Cy4P1+) and tetrakis [tris (dimethylamino) phosphonoamino] phosphazene (P5+). The effects of substituents on the polymerization behavior, especially the molecular weight and its distribution, degree of unsaturation, and the sequential structures of poly (propylene oxide) (PPO) were investigated. The structures of these catalysts and PPOs were characterized by FT-IR, 1H and 13C NMR, and GPC. The results indicate that Cy4P1+, Py4P1+, and Pi4P1+ have lower optimum reaction temperatures at 90, 70, and 70 °C, respectively, and are better than traditional catalysts KOH and double metal cyanide. PPO samples with high molecular weight, narrow polydispersity, and high functionality were accessible when catalyzed with Cy4P1+, Pi4P1+, and P5+ at the optimum temperature. Notably, Pi4P1+ formed unimodal distribution PPO with 9000 g/mol, 2.93 of functionality, and 0.008 mmol/g degree of unsaturation. Majority segments of PPO from five catalysts adopted the stereoregular head-to-tail structure, exhibiting excellent regularity.

Preparation of a Highly Fluorophilic Phosphonium Salt and its Use in a Fluorous Anion-Exchanger Membrane with High Selectivity for Perfluorinated Acids

PubMed Central

Boswell, Paul G.; Anfang, Alyce C.; Bühlmann, Philippe

2008-01-01

Fluorous solvents are the most nonpolar, nonpolarizable phases known, whereas ions are inherently polar. This makes it difficult to create salts that are soluble in a fluorous solvent. Here we present the synthesis and characterization of a new fluorophilic phosphonium salt, tris{3,5-bis[(perfluorooctyl)propyl]phenyl}methylphosphonium methyl sulfate. The salt has a solubility of at least 14 mM in perfluoro(perhydrophenanthrene), perfluoro(methylcyclohexane), and perfluorohexanes. It also shows immediate potential for use as a phase-transfer catalyst in fluorous biphasic catalysis, but in this work it is used as an anion exchanger site in the first potentiometric fluorous-membrane anion-selective electrode. The membrane sensor exhibited the exceptional selectivity of 3.9 × 1010 to 1 for perfluorooctanesulfonate over chloride, and of 2.5 × 107 to 1 for perfluorooctanoate over chloride. With improvements to the sensor’s detection limit and lifetime, it has the potential to be an attractive alternative to the expensive, time-consuming methods currently employed for measurement of perfluorinated acids. PMID:22072222

Stability and thermophysical studies on deep eutectic solvent based carbon nanotube nanofluid

NASA Astrophysics Data System (ADS)

Chen, Yan Yao; Walvekar, Rashmi; Khalid, Mohammad; Shahbaz, Kaveh; Gupta, T. C. S. M.

2017-07-01

Commercial coolants such as water, ethylene glycol and triethylene glycol possess very low thermal conductivity, high vapor pressure, corrosion issues and low thermal stability thus limiting the thermal enhancement of the nanofluids. Thus, a new type of base fluid known as deep eutectic solvents (DESs) is proposed in this work as a potential substitute for the conventional base fluid due to their unique solvent properties such as low vapor pressure, high thermal stability, biodegradability and non-flammability. In this work, 33 different DESs derived from phosphonium halide salt and ammonium halide salts were synthesised. Carbon nantubes (CNTs) with different concentrations (0.01 wt%-0.08 wt%) were dispersed into DESs with the help of sonication. Stability of the nanofluids were determined using both qualitative (visual observation) and quantitative (UV spectroscopy) approach. In addition, thermo-physical properties such as thermal conductivity, specific heat, viscosity and density were investigated. The stability results indicated that phosphonium based DESs have higher stability (up to 4 d) as compared to ammonium-based DESs (up to 3 d). Thermal enhancement of 30% was observed for ammonium based DES-CNT nanofluid whereas negative thermal enhancement was observed in phosphonium based DES-CNT nanofluid.

Extraction of Biomolecules Using Phosphonium-Based Ionic Liquids + K3PO4 Aqueous Biphasic Systems

PubMed Central

Louros, Cláudia L. S.; Cláudio, Ana Filipa M.; Neves, Catarina M. S. S.; Freire, Mara G.; Marrucho, Isabel M.; Pauly, Jérôme; Coutinho, João A. P.

2010-01-01

Aqueous biphasic systems (ABS) provide an alternative and efficient approach for the extraction, recovery and purification of biomolecules through their partitioning between two liquid aqueous phases. In this work, the ability of hydrophilic phosphonium-based ionic liquids (ILs) to form ABS with aqueous K3PO4 solutions was evaluated for the first time. Ternary phase diagrams, and respective tie-lines and tie-lines length, formed by distinct phosphonium-based ILs, water, and K3PO4 at 298 K, were measured and are reported. The studied phosphonium-based ILs have shown to be more effective in promoting ABS compared to the imidazolium-based counterparts with similar anions. Moreover, the extractive capability of such systems was assessed for distinct biomolecules (including amino acids, food colourants and alkaloids). Densities and viscosities of both aqueous phases, at the mass fraction compositions used for the biomolecules extraction, were also determined. The evaluated IL-based ABS have been shown to be prospective extraction media, particularly for hydrophobic biomolecules, with several advantages over conventional polymer-inorganic salt ABS. PMID:20480041

Highly efficient one-pot labeling of new phosphonium cations with fluorine-18 as potential PET agents for myocardial perfusion imaging.

PubMed

Zhao, Zuoquan; Yu, Qian; Mou, Tiantian; Liu, Chang; Yang, Wenjiang; Fang, Wei; Peng, Cheng; Lu, Jie; Liu, Yu; Zhang, Xianzhong

2014-11-03

Lipophilic cations such as phosphonium salts can accumulate in mitochondria of heart in response to the negative inner-transmembrane potentials. Two phosphonium salts [(18)F]FMBTP and [(18)F]mFMBTP were prepared and evaluated as potential myocardial perfusion imaging (MPI) agents in this study. The cations were radiolabeled via a simplified one-pot method starting from [(18)F]fluoride and followed by physicochemical property tests, in vitro cellular uptake assay, ex vivo mouse biodistribution, and in vivo rat microPET imaging. The total radiosynthesis time was less than 60 min including HPLC purification. The [(18)F] labeled compounds were obtained in high radiolabeling yield (∼50%) and good radiochemical purity (>99%). Both compounds were electropositive, and their log P values at pH 7.4 were 1.16 ± 0.003 (n = 3) and 1.05 ± 0.01 (n = 3), respectively. Both [(18)F]FMBTP and [(18)F]mFMBTP had high heart uptake (25.24 ± 2.97% ID/g and 31.02 ± 0.33% ID/g at 5 min postinjection (p.i.)) in mice with good retention (28.99 ± 3.54% ID/g and 26.82 ± 3.46% ID/g at 120 min p.i.). From the PET images in rats, the cations exhibited high myocardium uptake and fast clearance from liver and small intestine to give high-contrast images across all time points. These phosphonium cations were radiosynthesized via a highly efficient one-pot procedure for potential MPI offering high heart accumulation and rapid nontarget clearance.

Methodology for in situ protection of aldehydes and ketones using trimethylsilyl trifluoromethanesulfonate and phosphines: selective alkylation and reduction of ketones, esters, amides, and nitriles.

PubMed

Yahata, Kenzo; Minami, Masaki; Yoshikawa, Yuki; Watanabe, Kei; Fujioka, Hiromichi

2013-01-01

A methodology for selective transformations of ketones, esters, Weinreb amides, and nitriles in the presence of aldehydes has been developed. The use of a combination of PPh(3)-trimethylsilyl trifluoromethanesulfonate (TMSOTf) promotes selective transformation of aldehydes to their corresponding, temporarily protected, O,P-acetal type phosphonium salts. Because, hydrolytic work-up following ensuing reactions of other carbonyl moieties in the substrates liberates the aldehyde moiety, a sequence involving aldehyde protection, transformation of other carbonyl groups, and deprotection can be accomplished in a one-pot manner. Furthermore, the use of PEt(3) instead of PPh(3) enables ketones to be converted in situ to their corresponding O,P-ketal type phosphonium salts and, consequently, selective transformations of esters, Weinreb amides, and nitriles in the presence of ketones can be performed. This methodology is applicable to various dicarbonyl compounds, including substrates that possess heteroaromatic skeletons and hydroxyl protecting groups.

Induction of thermotropic bicontinuous cubic phases in liquid-crystalline ammonium and phosphonium salts.

PubMed

Ichikawa, Takahiro; Yoshio, Masafumi; Hamasaki, Atsushi; Taguchi, Satomi; Liu, Feng; Zeng, Xiang-bing; Ungar, Goran; Ohno, Hiroyuki; Kato, Takashi

2012-02-08

Two series of wedge-shaped onium salts, one ammonium and the other phosphonium, having 3,4,5-tris(alkyloxy)benzyl moieties, exhibit thermotropic bicontinuous "gyroid" cubic (Cub(bi)) and hexagonal columnar liquid-crystalline (LC) phases by nanosegregation between ionophilic and ionophobic parts. The alkyl chain lengths on the cationic moieties, anion species, and alkyl chain lengths on the benzyl moieties have crucial effects on their thermotropic phase behavior. For example, triethyl-[3,4,5-tris(dodecyloxy)benzyl]ammonium hexafluorophosphate forms the thermotropic Ia3d Cub(bi) LC phase, whereas an analogous compound with trifluoromethanesulfonate anion shows no LC properties. Synchrotron small-angle diffraction intensities from the Ia3d Cub(bi) LC materials provide electron density maps in the bulk state. The resulting maps show convincingly that the Ia3d Cub(bi) structure is composed of three-dimensionally interconnected ion nanochannel networks surrounded by aliphatic domains. A novel differential mapping technique has been applied successfully. The map of triethyl-[3,4,5-tris(decyloxy)benzyl]ammonium tetrafluoroborate has been subtracted from that of the analogous ammonium salt with hexafluorophosphate anion in the Ia3d Cub(bi) phases. The differential map shows that the counteranions are located in the core of the three-dimensionally interconnected nanochannel networks. Changing from trimethyl- via triethyl- to tripropylammonium cation changes the phase from columnar to Cub(bi) to no mesophase, respectively. This sensitivity to the widened shape for the narrow end of the molecule is explained successfully by the previously proposed semiquantitative geometric model based on the radial distribution of volume in wedge-shaped molecules. The LC onium salts dissolve lithium tetrafluoroborate without losing the Ia3d Cub(bi) LC phase. The Cub(bi) LC materials exhibit efficient ion-transporting behavior as a result of their 3D interconnected ion nanochannel networks. The Ia3d Cub(bi) LC material formed by triethyl-[3,4,5-tris(decyloxy)benzyl]phosphonium tetrafluoroborate shows ionic conductivities higher than the analogous Ia3d Cub(bi) material based on ammonium salts. The present study indicates great potential of Cub(bi) LC nanostructures consisting of ionic molecules for development of transportation nanochannel materials.

Induced amphotropic and thermotropic ionic liquid crystallinity in phosphonium halides: "lubrication" by hydroxyl groups.

PubMed

Ma, Kefeng; Somashekhar, B S; Gowda, G A Nagana; Khetrapal, C L; Weiss, Richard G

2008-03-18

The influence of covalently attaching hydroxymethylene to the methyl groups of methyl-tri-n-alkylphosphonium halides (where the alkyl chains are decyl, tetradecyl, or octadecyl and the halide is chloride or bromide) or adding methanol as a solute to the salts on their solid, liquid-crystalline (smectic A2), and isotropic phases has been investigated using a variety of experimental techniques. These structural and compositional changes are found to induce liquid crystallinity in some cases and to enhance the temperature range and lower the onset temperature of the liquid-crystalline phases in some others. The results are interpreted in terms of the lengths of the three n-alkyl chains attached to the phosphorus cation, the nature of the halide anion, the influence of H-bonding interactions at the head group regions of the layered phases, and other solvent-solute interactions. The fact that at least 1 molar equiv of methanol must be added to effect complete (isothermal) conversion of a solid methyl-tri-n-alkylphosphonium salt to a liquid crystal demonstrates a direct and strong association between individual methanol molecules and the phosphonium salts. Possible applications of such systems are suggested.

Antisense Oligodeoxynucleotide Inhibition of HIV Gene Expression

DTIC Science & Technology

1989-03-20

synthesis using trimethoxybenzyl side chain protection for Gln, the highly efficient benzotriazolyloxy tris(dimethylamino) phosphonium hexafluorophosphate ...0 - P - 0 -0 - O - - OH + Li OLi OLi OLi R 0 Fig. 11. Fai.t atom bombardment ma.ss spectroscopy of the lithium salt of 5’-trityl-CUAA, sputtered from

Analysis of quaternary ammonium and phosphonium ionic liquids by reversed-phase high-performance liquid chromatography with charged aerosol detection and unified calibration.

PubMed

Stojanovic, Anja; Lämmerhofer, Michael; Kogelnig, Daniel; Schiesel, Simone; Sturm, Martin; Galanski, Markus; Krachler, Regina; Keppler, Bernhard K; Lindner, Wolfgang

2008-10-31

Several hydrophobic ionic liquids (ILs) based on long-chain aliphatic ammonium- and phosphonium cations and selected aromatic anions were analyzed by reversed-phase high-performance liquid chromatography (RP-HPLC) employing trifluoroacetic acid as ion-pairing additive to the acetonitrile-containing mobile phase and adopting a step-gradient elution mode. The coupling of charged aerosol detection (CAD) for the non-chromophoric aliphatic cations with diode array detection (DAD) for the aromatic anions allowed their simultaneous analysis in a set of new ILs derived from either tricaprylmethylammonium chloride (Aliquat 336) and trihexyltetradecylphosphonium chloride as precursors. Aliquat 336 is a mix of ammonium cations with distinct aliphatic chain lengths. In the course of the studies it turned out that CAD generates an identical detection response for all the distinct aliphatic cations. Due to lack of single component standards of the individual Aliquat 336 cation species, a unified calibration function was established for the quantitative analysis of the quaternary ammonium cations of the ILs. The developed method was validated according to ICH guidelines, which confirmed the validity of the unified calibration. The application of the method revealed molar ratios of cation to anion close to 1 indicating a quantitative exchange of the chloride ions of the precursors by the various aromatic anions in the course of the synthesis of new ILs. Anomalies of CAD observed for the detection of some aromatic anions (thiosalicylate and benzoate) are discussed.

Development of a dispersive liquid-liquid microextraction method using a lighter-than-water ionic liquid for the analysis of polycyclic aromatic hydrocarbons in water.

PubMed

Medina, Giselle S; Reta, Mario

2016-11-01

A dispersive liquid-liquid microextraction method using a lighter-than-water phosphonium-based ionic liquid for the extraction of 16 polycyclic aromatic hydrocarbons from water samples has been developed. The extracted compounds were analyzed by liquid chromatography coupled to fluorescence/diode array detectors. The effects of several experimental parameters on the extraction efficiency, such as type and volume of ionic liquid and disperser solvent, type and concentration of salt in the aqueous phase and extraction time, were investigated and optimized. Three phosphonium-based ionic liquids were assayed, obtaining larger extraction efficiencies when trihexyl-(tetradecyl)phosphonium bromide was used. The optimized methodology requires a few microliters of a lighter-than-water phosphonium-based ionic liquid, which allows an easy separation of the extraction solvent phase. The obtained limits of detection were between 0.02 and 0.56 μg/L, enrichment factors between 109 and 228, recoveries between 60 and 108%, trueness between 0.4 and 9.9% and reproducibility values between 3 and 12% were obtained. These figures of merit combined with the simplicity, rapidity and low cost of the analytical methodology indicate that this is a viable and convenient alternative to the methods reported in the literature. The developed method was used to analyze polycyclic aromatic hydrocarbons in river water samples. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

From Broad-Spectrum Biocides to Quorum Sensing Disruptors and Mussel Repellents: Antifouling Profile of Alkyl Triphenylphosphonium Salts

PubMed Central

Martín-Rodríguez, Alberto J.; Babarro, Jose M. F.; Lahoz, Fernando; Sansón, Marta; Martín, Víctor S.; Norte, Manuel; Fernández, José J.

2015-01-01

‘Onium’ compounds, including ammonium and phosphonium salts, have been employed as antiseptics and disinfectants. These cationic biocides have been incorporated into multiple materials, principally to avoid bacterial attachment. In this work, we selected 20 alkyl-triphenylphosphonium salts, differing mainly in the length and functionalization of their alkyl chains, in fulfilment of two main objectives: 1) to provide a comprehensive evaluation of the antifouling profile of these molecules with relevant marine fouling organisms; and 2) to shed new light on their potential applications, beyond their classic use as broad-spectrum biocides. In this regard, we demonstrate for the first time that these compounds are also able to act as non-toxic quorum sensing disruptors in two different bacterial models (Chromobacterium violaceum and Vibrio harveyi) as well as repellents in the mussel Mytilus galloprovincialis. In addition, their inhibitory activity on a fouling-relevant enzymatic model (tyrosinase) is characterized. An analysis of the structure-activity relationships of these compounds for antifouling purposes is provided, which may result useful in the design of targeted antifouling solutions with these molecules. Altogether, the findings reported herein provide a different perspective on the biological activities of phosphonium compounds that is particularly focused on, but, as the reader will realize, is not limited to their use as antifouling agents. PMID:25897858

Design of Phosphonium-Type Zwitterion as an Additive to Improve Saturated Water Content of Phase-Separated Ionic Liquid from Aqueous Phase toward Reversible Extraction of Proteins

PubMed Central

Ito, Yoritsugu; Kohno, Yuki; Nakamura, Nobuhumi; Ohno, Hiroyuki

2013-01-01

We designed phosphonium-type zwitterion (ZI) to control the saturated water content of separated ionic liquid (IL) phase in the hydrophobic IL/water biphasic systems. The saturated water content of separated IL phase, 1-butyl-3-methyimidazolium bis(trifluoromethanesulfonyl)imide, was considerably improved from 0.4 wt% to 62.8 wt% by adding N,N,N-tripentyl-4-sulfonyl-1-butanephosphonium-type ZI (P555C4S). In addition, the maximum water content decreased from 62.8 wt% to 34.1 wt% by increasing KH2PO4/K2HPO4 salt content in upper aqueous phosphate buffer phase. Horse heart cytochrome c (cyt.c) was dissolved selectively in IL phase by improving the water content of IL phase, and spectroscopic analysis revealed that the dissolved cyt.c retained its higher ordered structure. Furthermore, cyt. c dissolved in IL phase was re-extracted again from IL phase to aqueous phase by increasing the concentration of inorganic salts of the buffer solution. PMID:24013379

Evaluation of chitosan quaternary ammonium salt-modified resin denture base material.

PubMed

Song, Rong; Zhong, Zhaohua; Lin, Lexun

2016-04-01

Chitosan quaternary ammonium salt displays good antioxidant and antibacterial characteristics and it shows appreciable solubility in water. When added to the traditional denture material to form a resin base, it could promote good oral health by improving the oral environment. In this study, chitosan quaternary ammonium salt was added to the denture material following two different methods. After three months of immersion in artificial saliva, the specimens were tested for tensile strength and were scanned by electron microscope. The murine fibroblast cytotoxicity and antibacterial properties were also tested. The result showed no significant differences in the tensile strength and in the proliferation of murine L929 fibroblast cells. The two structures of chitosan quaternary ammonium salt-modified denture material had different degrees of corrosion resistance and antimicrobial properties. These results indicate that chitosan quaternary ammonium salt-modified resin denture base material has the potential to become a new generation oral denture composite material. Copyright © 2015 Elsevier B.V. All rights reserved.

The competition of charge remote and charge directed fragmentation mechanisms in quaternary ammonium salt derivatized peptides--an isotopic exchange study.

PubMed

Cydzik, Marzena; Rudowska, Magdalena; Stefanowicz, Piotr; Szewczuk, Zbigniew

2011-12-01

Derivatization of peptides as quaternary ammonium salts (QAS) is a promising method for sensitive detection by electrospray ionization tandem mass spectrometry (Cydzik et al. J. Pept. Sci. 2011, 17, 445-453). The peptides derivatized by QAS at their N-termini undergo fragmentation according to the two competing mechanisms - charge remote (ChR) and charge directed (ChD). The absence of mobile proton in the quaternary salt ion results in ChR dissociation of a peptide bond. However, Hofmann elimination of quaternary salt creates an ion with one mobile proton leading to the ChD fragmentation. The experiments on the quaternary ammonium salts with deuterated N-alkyl groups or amide NH bonds revealed that QAS derivatized peptides dissociate according to the mixed ChR-ChD mechanism. The isotopic labeling allows differentiation of fragments formed according to ChR and ChD mechanisms. © The Author(s) 2011. This article is published with open access at Springerlink.com

Microorganisms as Analytical Indicators. Experimental Methods and Techniques,

DTIC Science & Technology

1980-01-01

Representa- tives of the genera Bacillus, Micrococcus, Escherichia, Pseudomonas, Aspergillus , and Penicillium are most frequently encountered...necessary for synthesis of prodigiosin, and magnesium is required for synthesis of bacteriochlorophylls. A change in the color of aspergillus spores...mesentericus niger and Bac. subtilis niger as a function of the concentration of phosphonium salts in the nutrient medium. The degree of

Selective coupling of methotrexate to peptide hormone carriers through a gamma-carboxamide linkage of its glutamic acid moiety: benzotriazol-1-yloxytris(dimethylamino)phosphonium hexafluorophosphate activation in salt coupling.

PubMed Central

Nagy, A; Szoke, B; Schally, A V

1993-01-01

A convenient synthetic method is described for the preparation of peptide-methotrexate (MTX) conjugates in which MTX is coupled selectively through the gamma-carboxyl group of its glutamic acid moiety to a free amino group in peptide analogs. The syntheses of a somatostatin analog-MTX conjugate (MTX-D-Phe-Cys-Tyr-D-Trp-Lys-Val-Cys-Thr-NH2) (AN-51) and two conjugates of analogs of luteinizing hormone-releasing hormone (LH-RH) with MTX [Glp-His-Trp-Ser-Tyr-D-Lys(MTX)-Leu-Arg-Pro-Gly-NH2] (AJ-04) and [Ac-Ser-Tyr-D-Lys(MTX)-Leu-Arg-Pro-NH-Et] AJ-51 are presented as examples. Benzotriazol-1-yloxytris(dimethylamino)phosphonium hexafluorophosphate (BOP reagent) was used in the synthesis for activation of 4-amino-4-deoxy-N10-methylpteroic acid, which reacted with the potassium salt of glutamic acid alpha-tert-butyl ester in dimethyl sulfoxide to form the suitably protected MTX derivative. This synthesis provides an example of the high suitability of BOP reagent for the salt-coupling method. The selectively protected MTX derivative was then coupled to the different peptide carriers and deprotected under relatively mild conditions by trifluoroacetic acid. The conjugates of MTX with hormonal analogs are suitable for targeting to various tumors that possess receptors for the peptide moieties. PMID:8101004

Lipophilic polyelectrolyte gel derived from phosphonium borate can absorb a wide range of organic solvents.

PubMed

Sunaga, Sokuro; Kokado, Kenta; Sada, Kazuki

2018-01-24

Herein, we demonstrate a polyelectrolyte gel which can absorb a wide range of organic solvents from dimethylsulfoxide (DMSO, permittivity: ε = 47.0) to tetrahydrofuran (ε = 5.6). The gel consists of polystyrene chains with small amounts (∼5 mol%) of lipophilic electrolytes derived from triphenylphosphonium tetraaryl borate. The swelling ability of the polyelectrolyte gel was higher than that of the alkyl ammonium tetraaryl borate previously reported by us, and this is attributed to the higher compatibility with organic solvents, as well as the higher dissociating ability, of the triphenyl phosphonium salt. The role of the ionic moieties was additionally confirmed by post modification of the polyelectrolyte gel via a conventional Wittig reaction, resulting in a nonionic gel. Our findings introduced here will lead to a clear-cut molecular design for polyelectrolyte gels which absorb all solvents.

Small quaternary alkyl phosphonium bis(fluorosulfonyl)imide ionic liquid electrolytes for sodium-ion batteries with P2- and O3-Na2/3[Fe2/3Mn1/3]O2 cathode material

NASA Astrophysics Data System (ADS)

Hilder, Matthias; Howlett, Patrick C.; Saurel, Damien; Gonzalo, Elena; Armand, Michel; Rojo, Teófilo; Macfarlane, Douglas R.; Forsyth, Maria

2017-05-01

A saturated solution of 2.3 M sodium bis(fluorosulfonyl)imide in trimethyl iso-butyl phosphonium bis(fluorosulfonyl)imide ionic liquid shows a high conductivity (0.94 mScm-1 at 50 °C), low ion association, and a wide operational temperature window (-71 °C-305 °C) making it a promising electrolyte for sodium battery applications. Cycling with P2- and O3-Na2/3[Fe2/3Mn1/3]O2 cathode display excellent performance at 50 °C outperforming conventional organic solvent based electrolytes in terms of capacities (at C/10) and long term cycle stability (at C/2). Post analysis of the electrolyte shows no measurable changes while the sodium metal anode and the cathode surface shows the presence of electrolyte specific elements after cycling, suggesting the formation of a stabilizing solid electrolyte interface. Additionally, cycling changes the topography and particle morphology of the cathode. Thus, the electrolyte properties and cell performance match or outperform previously reported results with the additional benefit of replacing the hazardous and flammable organic solvent solutions commonly employed.

Synthesis of acid addition salt of delta-aminolevulinic acid from 5-bromo levulinic acid esters

DOEpatents

Moens, Luc

2003-06-24

A process of preparing an acid addition salt of delta-aminolevulinc acid comprising: a) dissolving a lower alkyl 5-bromolevulinate and hexamethylenetetramine in a solvent selected from the group consisting of water, ethyl acetate, chloroform, acetone, ethanol, tetrahydrofuran and acetonitrile, to form a quaternary ammonium salt of the lower alkyl 5-bromolevulinate; and b) hydrolyzing the quaternary ammonium salt with an inorganic acid to form an acid addition salt of delta-aminolevulinic acid.

The Onium Compounds

NASA Astrophysics Data System (ADS)

Tsarevsky, Nicolay V.; Slaveykova, Vera; Manev, Stefan; Lazarov, Dobri

1997-06-01

The onium salts are of a big interest for theoretical and structural chemistry, and for organic synthesis. Some representatives of the group (e.g. ammonium salts) were known from the oldest times. Many onium salts are met the nature: ammonium salts (either as inorganic salts, and organic derivatives, e.g. aminoacids, salts of biogenic amines and alkaloids, etc.); oxonium salts (plant pigments as anthocyans are organic oxonium compounds), etc. In 1894 C. Hartmann and V. Meyer prepared the first iodonium salts - 4-iododiphenyliodonium hydrogensulfate and diphenyliodonium salts, and suggested the ending -onium for all compounds with properties similar to those of ammonium salts. Nowadays onium compounds of almost all nonmetals are synthesised and studied. A great variety of physical methods: diffraction (e.g. XRD) and spectral methods (IR-, NMR-, and UV-spectra), as well as the chemical properties and methods of preparation of onium salts have been used in determination of the structure of these compounds. The application of different onium salts is immense. Ammonium, phosphonium and sulfonium salts are used as phase-transfer catalysts; diazonium salts - for the preparation of dyes, metalochromic and pH-indicators. All the onium salts and especially diazonium and iodonium salts are very useful reagents in organic synthesis.

40 CFR 721.9075 - Quaternary ammonium salt of fluorinated alkylaryl amide.

Code of Federal Regulations, 2010 CFR

2010-07-01

... fluorinated alkylaryl amide. 721.9075 Section 721.9075 Protection of Environment ENVIRONMENTAL PROTECTION... amide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as quaternary ammonium salt of fluorinated alkylaryl amide (PMN No. P-92-688) is...

Curare-Like Activity of Mono-Quaternary Salts Containing Adamantyl Residue at the Nitrogen Atom

DTIC Science & Technology

As shown in previous works, mono-quaternary salts of alkamine esters of benzoic and cinnamic acids types and exhibit a pronounced curare like action...A series of methiodides of alkamine esters of benzoic and cinnamic acids were synthesized, containing at the quaternary nitrogen atom a 1-adamantyl...adamantyl causes a change of the substance’s mechanism of action, this applying both to the benzoic acid derivatives and to the cinnamic acid derivatives

Algicidal Activity of a Surface-Bonded Organosilicon Quaternary Ammonium Chloride

PubMed Central

Walters, P. A.; Abbott, E. A.; Isquith, A. J.

1973-01-01

The hydrolysis product of a quaternary amine-containing organosilicon salt, 3-(trimethoxysilyl)-propyldimethyloctadecyl ammonium chloride, was found to exhibit algicidal activity while chemically bonded to a variety of substrates. Six representative species of Chlorophyta, Cyanophyta, and Chrysophyta were used to evaluate the algicidal activity. Substrate-bonded 14C-labeled organosilicon quaternary ammonium salt when attached to nonwoven fibers was durable to repeated washings, and algicidal activity could not be attributed to slow release of the chemical. Images PMID:4632852

Versatile methods for synthesizing organic acid salts of quaternary berberine-type alkaloids as anti-ulcerative colitis agents.

PubMed

Zhang, Zhi-Hui; Li, Jing; Zhang, Hai-Jing; Deng, An-Jun; Wu, Lian-Qiu; Li, Zhi-Hong; Song, Hong-Rui; Wang, Wen-Jie; Qin, Hai-Lin

2016-06-01

Two versatile methods to synthesize kinds of organic acid salts of quaternary berberine-type alkaloids were investigated in order to determine which is more efficient to improve the liposolubility of the target compounds and to explore the efficacy of the target compounds as anti-ulcerative colitis (UC) agents. Overall evaluation according to the reaction results and yields of the final products indicated that the synthetic method using tertiary (±)-8-acylmethyldihydroberberine-type alkaloids as key intermediates is superior to that of using tertiary dihydroberberine-type alkaloids as intermediates. Ten target compounds were synthesized using quaternary berberine chloride and quaternary coptisine chloride as starting materials, respectively, and the anti-UC activity of some target compounds was evaluated in an in vitro x-box-binding protein 1 (XBP1) transcriptional activity assay using dual luciferase reporter detection. At 10 μM, the tested compounds were found to activate the transcription of XBP1 target at almost the same level as that of quaternary coptisine chloride. The synthesized target compounds were also found to share higher liposolubility than the inorganic acid salts of quaternary berberine-type alkaloid.

Room-temperature ionic liquids enhanced green synthesis of β-glycosyl 1-ester.

PubMed

Cui, Yanli; Xu, Minghan; Yao, Weirong; Mao, Jianwei

2015-04-30

We herein report an efficient synthesis of β-glycosyl 1-ester in room-temperature ionic liquids (RTILs) promoted via silver salt and quaternary ammonium salt (PTC) with good or excellent yields. All products were isolated exclusively as the β-anomers. Four different RTILs, eight metal salts and four quaternary ammonium salts were screened in the glycosylation reaction. The synergistic effect of C6mim·OTf, Ag2O and tetrabutylammonium iodine gave the best results. Their promotion to the system was integral. Thorough study provided insight into the catalytic activity of ionic liquid structure, metal salts and quaternary ammonium salt to these reactions. It is worth mentioning that the yield of aliphatic compound 2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl butyrate (3l) was highly improved when using C6mim·OTf as solvent compared with the normal volatile solvents under the same catalysts. This green approach has been proved to be practical and compatible with a wide range from aliphatic to aromatic substrates. Copyright © 2015 Elsevier Ltd. All rights reserved.

Surface modification and antimicrobial properties of cellulose nanocrystals

NASA Astrophysics Data System (ADS)

Bespalova, Yulia A.

Surface modification of cellulose nanocrystals (CNC) was performed by acetylation and subsequent reaction with various tertiary amines with different lengths of alkyl groups. Chloroacetic anhydride (95%) was used for acetylation. The acetylation of CNC was confirmed using IR spectroscopy. The bands associated with C=0 stretching (1740 cm-1) and C-Cl stretching (793 cm -1) was present in the acetylated CNC but they were absent in the neat CNC. It has been suggested that the primary hydroxyl groups of CNC are substituted by chloro acetyl groups during acetylation reaction. Subsequent reaction of chloro acetylated CNC with N, N - Dimethyl ethylamine, N, N - Dimethyl hexylamine, N, N - Dimethyl dodecylamine, N, N - Dimethyl hexadecylamine and N, N - Dimethyl decylamine formed quaternary ammonium salts. These quaternary ammonium salts were characterized by FTIR and solid state13C NMR spectroscopy. FTIR spectra of five types of quaternary ammonium salts of CNC are similar and they showed infrared bands at 2905 -1 and 2850 cm-1, attributed to symmetrical and unsymmetrical C-H stretching vibration. The absence of C-Cl band at 793 cm-1 proves that quaternary salt formation was successful. The 13C NMR spectrum of quaternary ammonium modified CNC with N, N - Dimethyl dodecylamine shows several additional resonances ranging from 14.5 ppm to 58.0 ppm when compared to 13C NMR spectrum of pure CNC. This evidence proves that long alkyl chains have been added to the pure CNC. The disc diffusion method confirmed that quaternary ammonium modified CNCs with a chain longer than ten carbons are effective antimicrobial agents against Staphylococcus aureus and E. coli bacteria. Pure CNC and quaternary ammonium modified CNCs with an alkyl chain length of ten or less were not able to inhibit bacteria growth.

Advances in Nucleophilic Phosphine Catalysis of Alkenes, Allenes, Alkynes, and MBHADs

PubMed Central

Fan, Yi Chiao

2014-01-01

In nucleophilic phosphine catalysis, tertiary phosphines undergo conjugate additions to activated carbon–carbon multiple bonds to form β-phosphonium enolates, β-phosphonium dienolates, β-phosphonium enoates, and vinyl phosphonium ylides as intermediates. When these reactive zwitterionic species react with nucleophiles and electrophiles, they may generate carbo- and heterocycles with multifarious molecular architectures. This Article describes the reactivities of these phosphonium zwitterions, the applications of phosphine catalysis in the syntheses of biologically active compounds and natural products, and recent developments in the enantioselective phosphine catalysis. PMID:24196409

Derivatization of peptides as quaternary ammonium salts for sensitive detection by ESI-MS.

PubMed

Cydzik, Marzena; Rudowska, Magdalena; Stefanowicz, Piotr; Szewczuk, Zbigniew

2011-06-01

A series of model peptides in the form of quaternary ammonium salts at the N-terminus was efficiently prepared by the solid-phase synthesis. Tandem mass spectrometric analysis of the peptide quaternary ammonium derivatives was shown to provide sequence confirmation and enhanced detection. We designed the 2-(1,4-diazabicyclo[2.2.2] octylammonium)acetyl quaternary ammonium group which does not suffer from neutral losses during MS/MS experiments. The presented quaternization of 1,4-diazabicyclo[2.2.2]octane (DABCO) by iodoacetylated peptides is relatively easy and compatible with standard solid-phase peptide synthesis. This methodology offers a novel sensitive approach to analyze peptides and other compounds. Copyright © 2011 European Peptide Society and John Wiley & Sons, Ltd.

Pesticide Removal from Aqueous Solutions by Adding Salting Out Agents

PubMed Central

Moscoso, Fátima; Deive, Francisco J.; Esperança, José M. S. S.; Rodríguez, Ana

2013-01-01

Phase segregation in aqueous biphasic systems (ABS) composed of four hydrophilic ionic liquids (ILs): 1-butyl-3-methylimidazolium methylsulfate and 1-ethyl-3-methylimidazolium methylsulfate (CnC1im C1SO4, n = 2 and 4), tributylmethyl phosphonium methylsulfate (P4441 C1SO4) and methylpyridinium methylsulfate (C1Py C1SO4) and two high charge density potassium inorganic salts (K2CO3 and K2HPO4) were determined by the cloud point method at 298.15 K. The influence of the addition of the selected inorganic salts to aqueous mixtures of ILs was discussed in the light of the Hofmeister series and in terms of molar Gibbs free energy of hydration. The effect of the alkyl chain length of the cation on the methylsulfate-based ILs has been investigated. All the solubility data were satisfactorily correlated to several empirical equations. A pesticide (pentachlorophenol, PCP) extraction process based on the inorganic salt providing a greater salting out effect was tackled. The viability of the proposed process was analyzed in terms of partition coefficients and extraction efficiencies. PMID:24145747

Effects of Detergent β-Octylglucoside and Phosphate Salt Solutions on Phase Behavior of Monoolein Mesophases

PubMed Central

Khvostichenko, Daria S.; Ng, Johnathan J.D.; Perry, Sarah L.; Menon, Monisha; Kenis, Paul J.A.

2013-01-01

Using small-angle x-ray scattering (SAXS), we investigated the phase behavior of mesophases of monoolein (MO) mixed with additives commonly used for the crystallization of membrane proteins from lipidic mesophases. In particular, we examined the effect of sodium and potassium phosphate salts and the detergent β-octylglucoside (βOG) over a wide range of compositions relevant for the crystallization of membrane proteins in lipidic mesophases. We studied two types of systems: 1), ternary mixtures of MO with salt solutions above the hydration boundary; and 2), quaternary mixtures of MO with βOG and salt solutions over a wide range of hydration conditions. All quaternary mixtures showed highly regular lyotropic phase behavior with the same sequence of phases (Lα, Ia3d, and Pn3m) as MO/water mixtures at similar temperatures. The effects of additives in quaternary systems agreed qualitatively with those found in ternary mixtures in which only one additive is present. However, quantitative differences in the effects of additives on the lattice parameters of fully hydrated mesophases were found between ternary and quaternary mixtures. We discuss the implications of these findings for mechanistic investigations of membrane protein crystallization in lipidic mesophases and for studies of the suitability of precipitants for mesophase-based crystallization methods. PMID:24138861

Ionic liquids containing symmetric quaternary phosphonium cations and phosphorus-containing anions, and their use as lubricant additives

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qu, Jun; Luo, Huimin

An ionic liquid composition having the following generic structural formula: ##STR00001## wherein R 1, R 2, R 3, and R 4 are equivalent and selected from hydrocarbon groups containing at least three carbon atoms, and X - is a phosphorus-containing anion, particularly an organophosphate, organophosphonate, or organophosphinate anion, or a thio-substituted analog thereof containing hydrocarbon groups with at least three carbon atoms. Also described are lubricant compositions comprising the above ionic liquid and a base oil, wherein the ionic liquid is dissolved in the base oil. Further described are methods for applying the ionic liquid or lubricant composition onto amore » mechanical device for which lubrication is beneficial, with resulting improvement in friction reduction, wear rate, and/or corrosion inhibition.« less

Incorporation of quaternary ammonium salts containing different counterions to improve the performance of inverted perovskite solar cells

NASA Astrophysics Data System (ADS)

Yan, Po-Ruei; Huang, Wei-Jie; Yang, Sheng-Hsiung

2017-02-01

In this research, three quaternary ammonium salts containing different counterions, including tetrabutylammonium bromide (TBABr), tetrabutylammonium tetrafluoroborate (TBABF4), and tetrabutylammonium hexafluorophosphate (TBAPF6), were incorporated into [6,6]-phenyl-C61 butyric acid methyl ester (PCBM) as electron transporting layer (ETL). These salts-doped PCBM films revealed higher electron mobility and Fermi levels compared with the un-doped one. Better charge transfer at the interface between perovskite and salts-doped PCBM was also obtained from PL quenching experiments. Inverted perovskite solar cells with the configuration of ITO/PEDOT:PSS/CH3NH3PbI3/PCBM + salts/Ag were fabricated, and the JSC and FF of devices were significantly enhanced using salts-doped PCBM as ETL. The best device based on TBABF4-doped PCBM delivered a power conversion efficiency (PCE) up to 13.41%, which was superior to the one with undoped PCBM layer (PCE = 8.77%).

40 CFR 721.10666 - Quaternary ammonium compounds, bis(fattyalkyl) dimethyl, salts with tannins (generic).

Code of Federal Regulations, 2014 CFR

2014-07-01

...(fattyalkyl) dimethyl, salts with tannins (generic). 721.10666 Section 721.10666 Protection of Environment..., bis(fattyalkyl) dimethyl, salts with tannins (generic). (a) Chemical substance and significant new... compounds, bis(fattyalkyl) dimethyl, salts with tannins (PMN P-12-437) is subject to reporting under this...

40 CFR 721.10666 - Quaternary ammonium compounds, bis(fattyalkyl) dimethyl, salts with tannins (generic).

Code of Federal Regulations, 2013 CFR

2013-07-01

...(fattyalkyl) dimethyl, salts with tannins (generic). 721.10666 Section 721.10666 Protection of Environment..., bis(fattyalkyl) dimethyl, salts with tannins (generic). (a) Chemical substance and significant new... compounds, bis(fattyalkyl) dimethyl, salts with tannins (PMN P-12-437) is subject to reporting under this...

In situ analysis of corrosion inhibitors using a portable mass spectrometer with paper spray ionization.

PubMed

Jjunju, Fred P M; Li, Anyin; Badu-Tawiah, Abraham; Wei, Pu; Li, Linfan; Ouyang, Zheng; Roqan, Iman S; Cooks, R Graham

2013-07-07

Paper spray (PS) ambient ionization is implemented using a portable mass spectrometer and applied to the detection of alkyl quaternary ammonium salts in a complex oil matrix. These salts are commonly used as active components in the formulation of corrosion inhibitors. They were identified in oil and confirmed by their fragmentation patterns recorded using tandem mass spectrometry (MS/MS). The cations of alkyl and benzyl-substituted quaternary ammonium salts showed characteristic neutral losses of CnH2n (n carbon number of the longest chain) and C7H8, respectively. Individual quaternary ammonium compounds were detected at low concentrations (<1 ng μL(-1)) and over a dynamic range of ∼5 pg μL(-1) to 500 pg μL(-1) (ppb). Direct detection of these compounds in complex oil samples without prior sample preparation or pre-concentration was also demonstrated using a home-built miniature mass spectrometer at levels below 1 ng μL(-1).

Solid State Synthesis Under Supramolecular Control of a 2D Heterotetratopic Self-complementary Tecton Tailored to Halogen Bonding

DTIC Science & Technology

2006-07-31

BuLi . A 96 : 4 mixture of trans : cis isomers was obtained in 84% overall yield; stereoisomers were easily separated by chroma- tography. Iodination of...the tetrafluorobenzene group12 was carried out with n- BuLi –I2 in THF affording 4 in 85% yield (Scheme 1). Orange-yellow prismatic crystals have been...mmol) of phosphonium salt 1 were suspended in 1 mL of THF at 70 1C. 0.7 mmol of n- BuLi (1.6 M) were added and the mixture was warmed up to room

Partition coefficients of organic compounds between water and imidazolium-, pyridinium-, and phosphonium-based ionic liquids.

PubMed

Padró, Juan M; Pellegrino Vidal, Rocío B; Reta, Mario

2014-12-01

The partition coefficients, P IL/w, of several compounds, some of them of biological and pharmacological interest, between water and room-temperature ionic liquids based on the imidazolium, pyridinium, and phosphonium cations, namely 1-octyl-3-methylimidazolium hexafluorophosphate, N-octylpyridinium tetrafluorophosphate, trihexyl(tetradecyl)phosphonium chloride, trihexyl(tetradecyl)phosphonium bromide, trihexyl(tetradecyl)phosphonium bis(trifluoromethylsulfonyl)imide, and trihexyl(tetradecyl)phosphonium dicyanamide, were accurately measured. In this way, we extended our database of partition coefficients in room-temperature ionic liquids previously reported. We employed the solvation parameter model with different probe molecules (the training set) to elucidate the chemical interactions involved in the partition process and discussed the most relevant differences among the three types of ionic liquids. The multiparametric equations obtained with the aforementioned model were used to predict the partition coefficients for compounds (the test set) not present in the training set, most being of biological and pharmacological interest. An excellent agreement between calculated and experimental log P IL/w values was obtained. Thus, the obtained equations can be used to predict, a priori, the extraction efficiency for any compound using these ionic liquids as extraction solvents in liquid-liquid extractions.

New molten salt systems for high temperature molten salt batteries: Ternary and quaternary molten salt systems based on LiF-LiCl, LiF-LiBr, and LiCl-LiBr

NASA Astrophysics Data System (ADS)

Fujiwara, Syozo; Inaba, Minoru; Tasaka, Akimasa

Using a new simulative technique developed by us, we systematically investigated new ternary or quaternary molten salt systems, which are based on LiF-LiCl, LiF-LiBr, and LiCl-LiBr binary systems, for use as electrolytes in thermal batteries, and evaluated their ionic conductivities and melting points experimentally. It was confirmed experimentally that LiF-LiBr-KF (melting point: 425 °C, ionic conductivity at 500 °C: 2.52 S cm -1), LiCl-LiBr-KF (405 °C, 2.56 S cm -1), LiCl-LiBr-NaF-KF (425 °C, 3.11 S cm -1), LiCl-LiBr-NaCl-KCl (420 °C, 2.73 S cm -1), and LiCl-LiBr-NaBr-KBr (420 °C, 2.76 S cm -1) meet our targets for both melting point (350-430 °C) and ionic conductivity (2.0 S cm -1 and higher at 500 °C). A single cell using the newly developed LiCl-LiBr-NaCl-KCl molten salt as an electrolyte was prepared, and the DC-IR of the cell decreased by 20% than that of a single cell using the conventional LiCl-KCl molten salt. It was therefore concluded that the use of new quaternary molten salt systems can improve the discharge rate-capability in practical battery applications because of their high ionic conductivities.

Removal of Zn or Cd and cyanide from cyanide electroplating wastes

DOEpatents

Moore, Fletcher L.

1977-05-31

A method is described for the efficient stripping of stable complexes of a selected quaternary amine and a cyanide of Zn or Cd. An alkali metal hydroxide solution such as NaOH or KOH will quantitatively strip a pregnant extract of the quaternary ammonium complex of its metal and cyanide content and regenerate a quaternary ammonium hydroxide salt which can be used for extracting further metal cyanide values.

Separation of aromatic carboxylic acids using quaternary ammonium salts on reversed-phase HPLC. 2. Application for the analysis of Loy Yang coal oxidation products

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kawamura, K.; Okuwaki, A.; Verheyen, T.V.

In order to develop separation processes and analytical methods for aromatic carboxylic acids for the coal oxidation products, the separation behavior of aromatic carboxylic acids on a reversed-phase HPLC using eluent containing quaternary ammonium salt was optimized using the solvent gradient method. This method was applied for the analysis of Loy Yang coal oxidation products. It was confirmed that the analytical data using this method were consistent with those determined using gas chromatography.

Metal-organophosphine and metal-organophosphonium frameworks with layered honeycomb-like structures.

PubMed

Humphrey, Simon M; Allan, Phoebe K; Oungoulian, Shaunt E; Ironside, Matthew S; Wise, Erica R

2009-04-07

Phosphanotriylbenzenecarboxylic acid (ptbcH(3); P(C(6)H(4)-p-CO(2)H)(3)) and its methyl phosphonium iodide derivative (mptbcH(3)I; {H(3)CP(C(6)H(4)-p-CO(2)H)(3)}I) have been used as organic building blocks in reaction with Zn(ii) salts to obtain a series of related two-dimensional coordination polymers with honeycomb-like networks. The variable coordination number and oxidation states available to phosphorus have been exploited to produce a family of related phosphine coordination materials (PCMs) using a single ligand precursor. The phosphine carboxylate trianion, ptbc(3-), reacted with Zn(ii) to form 3,3-connected undulating hexagonal sheets based on tetrahedral P and Zn nodes, where Zn-ptbc = 1 : 1. When hydroxide was used as an additional framework ligand, Zn(4)(OH)(2) clusters were obtained. The clusters support 6,3-connected bilayers that consist of pairs of fused hexagonal sheets (Zn-ptbc = 2 : 1) with intra-layer pore spaces. The Zn(4)(OH)(2) clusters are also coordinated by solvent, which was preferentially displaced when the bilayer material was synthesized in the presence of ethylene diamine. Treatment of ptbc(3-) with MeI resulted in methylation of the phosphine to give the P(v) phosphonium iodide salt derivative. The formally dianionic methylphosphonium tricarboxylate building block, mptbc(2-), has the same trigonal-pyramidal bridging geometry as the parent phosphine. However, mptbc(2-) reacted with Zn(ii) on a 1 : 1 stoichiometric ratio to give an unusual trilayer sheet polymer that is based exclusively on 3-connected nodes. Solid-state (31)P NMR studies confirmed that the phosphine ligands were resistant to oxidation upon solvothermal reaction under aerobic conditions.

Reporter-free potentiometric sensing of boronic acids and their reactions by using quaternary ammonium salt-functionalized polymeric liquid membranes.

PubMed

Wang, Xuewei; Yue, Dengfeng; Lv, Enguang; Wu, Lei; Qin, Wei

2014-02-18

The tremendous applications of boronic acids (BAs) in chemical sensing, medical chemistry, molecular assembly, and organic synthesis lead to an urgent demand for developing effective sensing methods for BAs. This paper reports a facile and sensitive potentiometric sensor scheme for heterogeneous detection of BAs based on their unexpected potential responses on quaternary ammonium salt-doped polymeric liquid membranes. (11)B NMR data reveal that a quaternary ammonium chloride can trigger the hydrolysis of an electrically neutral BA in an aprotic solvent. Using the quaternary ammonium salt as the receptor, the BA molecules can be extracted from the sample solution into the polymeric membrane phase and undergo the concomitant hydrolysis. Such salt-triggered hydrolysis generates H(+) ions, which can be coejected into the aqueous phase with the counterions (e.g., Cl(-)) owing to their high hydrophilicities. The perturbation on the ionic partition at the sample-membrane interface changes the phase boundary potential and thus enables the potentiometric sensing of BAs. In contrast to other transduction methods for BAs, for which labeled or separate reporters are exclusively required, the present heterogeneous sensing scheme allows the direct detection of BAs without using any reporter molecules. This technique shows superior detection limits for BAs (e.g., 1.0 × 10(-6) M for phenylboronic acid) as compared to previously reported methods based on colorimetry, fluorimetry, and mass spectrometry. The proposed sensing strategy has also been successfully applied to potentiometric indication of the BA reactions with hydrogen peroxide and saccharides, which allows indirect and sensitive detection of these important species.

Theoretical problems associated with the use of acetic anhydride as a co-solvent for the non-aqueous titration of hydrohalides of organic bases and quaternary ammonium salts.

PubMed

Völgyi, Gergely; Béni, Szabolcs; Takács-Novák, Krisztina; Görög, Sándor

2010-01-05

A potentiometric titration study of organic base hydrohalides and quaternary ammonium salts using perchloric acid as the titrant and a mixture of acetic anhydride and acetic acid as the solvent was carried out and the titration mixture was analysed by NMR in order to clarify the chemistry of the reactions involved. It was found that in contrast to the general belief the formation of acetyl halides and titratable free acetate ion does not take place prior to the titration but NMR spectra proved the formation of acetyl halides in the course of the titration. This observation and the fact that the shape of the titration curves depends on the nature of the hydrohaloic acid bound to the base or of the anion in the quaternary ammonium salts led to the conclusion that the titrating agent is acetyl perchlorate formed in situ during the titration. Equations of the reactions involved in the titration process are shown in the paper.

A Novel Surface Structure Consisting of Contact-active Antibacterial Upper-layer and Antifouling Sub-layer Derived from Gemini Quaternary Ammonium Salt Polyurethanes.

PubMed

He, Wei; Zhang, Yi; Li, Jiehua; Gao, Yunlong; Luo, Feng; Tan, Hong; Wang, Kunjie; Fu, Qiang

2016-08-26

Contact-active antibacterial surfaces play a vital role in preventing bacterial contamination of artificial surfaces. In the past, numerous researches have been focused on antibacterial surfaces comprising of antifouling upper-layer and antibacterial sub-layer. In this work, we demonstrate a reversed surface structure which integrate antibacterial upper-layer and antifouling sub-layer. These surfaces are prepared by simply casting gemini quaternary ammonium salt waterborne polyurethanes (GWPU) and their blends. Due to the high interfacial energy of gemini quaternary ammonium salt (GQAS), chain segments containing GQAS can accumulate at polymer/air interface to form an antibacterial upper-layer spontaneously during the film formation. Meanwhile, the soft segments composed of polyethylene glycol (PEG) formed the antifouling sub-layer. Our findings indicate that the combination of antibacterial upper-layer and antifouling sub-layer endow these surfaces strong, long-lasting antifouling and contact-active antibacterial properties, with a more than 99.99% killing efficiency against both gram-positive and gram-negative bacteria attached to them.

Selective detection of carbohydrates and their peptide conjugates by ESI-MS using synthetic quaternary ammonium salt derivatives of phenylboronic acids.

PubMed

Kijewska, Monika; Kuc, Adam; Kluczyk, Alicja; Waliczek, Mateusz; Man-Kupisinska, Aleksandra; Lukasiewicz, Jolanta; Stefanowicz, Piotr; Szewczuk, Zbigniew

2014-06-01

We present new tags based on the derivatives of phenylboronic acid and apply them for the selective detection of sugars and peptide-sugar conjugates in mass spectrometry. We investigated the binding of phenylboronic acid and its quaternary ammonium salt (QAS) derivatives to carbohydrates and peptide-derived Amadori products by HR-MS and MS/MS experiments. The formation of complexes between sugar or sugar-peptide conjugates and synthetic tags was confirmed on the basis of the unique isotopic distribution resulting from the presence of boron atom. Moreover, incorporation of a quaternary ammonium salt dramatically improved the efficiency of ionization in mass spectrometry. It was found that the formation of a complex with phenylboronic acid stabilizes the sugar moiety in glycated peptides, resulting in simplification of the fragmentation pattern of peptide-derived Amadori products. The obtained results suggest that derivatization of phenylboronic acid as QAS is a promising method for sensitive ESI-MS detection of carbohydrates and their conjugates formed by non-enzymatic glycation or glycosylation.

Selective Detection of Carbohydrates and Their Peptide Conjugates by ESI-MS Using Synthetic Quaternary Ammonium Salt Derivatives of Phenylboronic Acids

NASA Astrophysics Data System (ADS)

Kijewska, Monika; Kuc, Adam; Kluczyk, Alicja; Waliczek, Mateusz; Man-Kupisinska, Aleksandra; Lukasiewicz, Jolanta; Stefanowicz, Piotr; Szewczuk, Zbigniew

2014-06-01

We present new tags based on the derivatives of phenylboronic acid and apply them for the selective detection of sugars and peptide-sugar conjugates in mass spectrometry. We investigated the binding of phenylboronic acid and its quaternary ammonium salt (QAS) derivatives to carbohydrates and peptide-derived Amadori products by HR-MS and MS/MS experiments. The formation of complexes between sugar or sugar-peptide conjugates and synthetic tags was confirmed on the basis of the unique isotopic distribution resulting from the presence of boron atom. Moreover, incorporation of a quaternary ammonium salt dramatically improved the efficiency of ionization in mass spectrometry. It was found that the formation of a complex with phenylboronic acid stabilizes the sugar moiety in glycated peptides, resulting in simplification of the fragmentation pattern of peptide-derived Amadori products. The obtained results suggest that derivatization of phenylboronic acid as QAS is a promising method for sensitive ESI-MS detection of carbohydrates and their conjugates formed by non-enzymatic glycation or glycosylation.

A Novel Surface Structure Consisting of Contact-active Antibacterial Upper-layer and Antifouling Sub-layer Derived from Gemini Quaternary Ammonium Salt Polyurethanes

PubMed Central

He, Wei; Zhang, Yi; Li, Jiehua; Gao, Yunlong; Luo, Feng; Tan, Hong; Wang, Kunjie; Fu, Qiang

2016-01-01

Contact-active antibacterial surfaces play a vital role in preventing bacterial contamination of artificial surfaces. In the past, numerous researches have been focused on antibacterial surfaces comprising of antifouling upper-layer and antibacterial sub-layer. In this work, we demonstrate a reversed surface structure which integrate antibacterial upper-layer and antifouling sub-layer. These surfaces are prepared by simply casting gemini quaternary ammonium salt waterborne polyurethanes (GWPU) and their blends. Due to the high interfacial energy of gemini quaternary ammonium salt (GQAS), chain segments containing GQAS can accumulate at polymer/air interface to form an antibacterial upper-layer spontaneously during the film formation. Meanwhile, the soft segments composed of polyethylene glycol (PEG) formed the antifouling sub-layer. Our findings indicate that the combination of antibacterial upper-layer and antifouling sub-layer endow these surfaces strong, long-lasting antifouling and contact-active antibacterial properties, with a more than 99.99% killing efficiency against both gram-positive and gram-negative bacteria attached to them. PMID:27561546

Hydrogeologic Framework of the Salt Basin, New Mexico and Texas

NASA Astrophysics Data System (ADS)

Ritchie, A. B.; Phillips, F. M.

2010-12-01

The Salt Basin is a closed drainage basin located in southeastern New Mexico (Otero, Chaves, and Eddy Counties), and northwestern Texas (Hudspeth, Culberson, Jeff Davis, and Presidio Counties), which can be divided into a northern and a southern system. Since the 1950s, extensive groundwater withdrawals have been associated with agricultural irrigation in the Dell City, Texas region, just south of the New Mexico-Texas border. Currently, there are three major applications over the appropriations of groundwater in the Salt Basin. Despite these factors, relatively little is known about the recharge rates and storage capacity of the basin, and the estimates that do exist are highly variable. The Salt Basin groundwater system was declared by the New Mexico State Engineer during 2002 in an attempt to regulate and control growing interest in the groundwater resources of the basin. In order to help guide long-term management strategies, a conceptual model of groundwater flow in the Salt Basin was developed by reconstructing the tectonic forcings that have affected the basin during its formation, and identifying the depositional environments that formed and the resultant distribution of facies. The tectonic history of the Salt Basin can be divided into four main periods: a) Pennsylvanian-to-Early Permian, b) Mid-to-Late Permian, c) Late Cretaceous, and d) Tertiary-to-Quaternary. Pennsylvanian-to-Permian structural features affected deposition throughout the Permian, resulting in three distinct hydrogeologic facies: basin, shelf-margin, and shelf. Permian shelf facies rocks form the primary aquifer within the northern Salt Basin, although minor aquifers occur in Cretaceous rocks and Tertiary-to-Quaternary alluvium. Subsequent tectonic activity during the Late Cretaceous resulted in the re-activation of many of the earlier structures. Tertiary-to-Quaternary Basin-and-Range extension produced the current physiographic form of the basin.

Aqueous biphasic systems containing PEG-based deep eutectic solvents for high-performance partitioning of RNA.

PubMed

Zhang, Hongmei; Wang, Yuzhi; Zhou, Yigang; Xu, Kaijia; Li, Na; Wen, Qian; Yang, Qin

2017-08-01

In this work, 16 kinds of novel deep eutectic solvents (DESs) composed of polyethylene glycol (PEG) and quaternary ammonium salts, were coupled with Aqueous Biphasic Systems (ABSs) to extract RNA. The phase forming ability of ABSs were comprehensively evaluated, involving the effects of various proportions of DESs' components, carbon chain length and anions species of quaternary ammonium salts, average molecular weights of PEG and inorganic salts nature. Then the systems were applied in RNA extraction, and the results revealed that the extraction efficiency values were distinctly enhanced by relatively lower PEG content in DESs, smaller PEG molecular weights, longer carbon chain of quaternary ammonium salts and more hydrophobic inorganic salts. Then the systems composed of [TBAB][PEG600] and Na 2 SO 4 were utilized in the influence factor experiments, proving that the electrostatic interaction was the dominant force for RNA extraction. Therefore, back-extraction efficiency values ranging between 85.19% and 90.78% were obtained by adjusting the ionic strength. Besides, the selective separation of RNA and tryptophane (Trp) was successfully accomplished. It was found that 86.19% RNA was distributed in the bottom phase, while 72.02% Trp was enriched in the top phase in the novel ABSs. Finally, dynamic light scattering (DLS) and transmission electron microscope (TEM) were used to further investigate the extraction mechanism. The proposed method reveals the outstanding feasibility of the newly developed ABSs formed by PEG-based DESs and inorganic salts for the green extraction of RNA. Copyright © 2017 Elsevier B.V. All rights reserved.

Phosphonium-based ionic liquids and uses

DOEpatents

Del Sesto, Rico E; Koppisch, Andrew T; Lovejoy, Katherine S; Purdy, Geraldine M

2014-12-30

Phosphonium-based room temperature ionic liquids ("RTILs") were prepared. They were used as matrices for Matrix-Assisted Laser Desorption Ionization (MALDI) mass spectrometry and also for preparing samples of dyes for analysis.

Late Quaternary Faulting in Southeastern Louisiana: A Natural Laboratory for Understanding Shallow Faulting in Deltaic Materials

NASA Astrophysics Data System (ADS)

Dawers, N. H.; McLindon, C.

2017-12-01

A synthesis of late Quaternary faults within the Mississippi River deltaic plain aims to provide a more accurate assessment of regional and local fault architecture, and interactions between faulting, sediment loading, salt withdrawal and compaction. This effort was initiated by the New Orleans Geological Society and has resulted in access to industry 3d seismic reflection data, as well as fault trace maps, and various types of well data and biostratigraphy. An unexpected outgrowth of this project is a hypothesis that gravity-driven normal faults in deltaic settings may be good candidates for shallow aseismic and slow-slip phenomena. The late Quaternary fault population is characterized by several large, highly segmented normal fault arrays: the Baton Rouge-Tepetate fault zone, the Lake Pontchartrain-Lake Borgne fault zone, the Golden Meadow fault zone (GMFZ), and a major counter-regional salt withdrawal structure (the Bay Marchand-Timbalier Bay-Caillou Island salt complex and West Delta fault zone) that lies just offshore of southeastern Louisiana. In comparison to the other, more northerly fault zones, the GMFZ is still significantly salt-involved. Salt structures segment the GMFZ with fault tips ending near or within salt, resulting in highly localized fault and compaction related subsidence separated by shallow salt structures, which are inherently buoyant and virtually incompressible. At least several segments within the GMFZ are characterized by marsh breaks that formed aseismically over timescales of days to months, such as near Adams Bay and Lake Enfermer. One well-documented surface rupture adjacent to a salt dome propagated over a 3 day period in 1943. We suggest that Louisiana's coastal faults make excellent analogues for deltaic faults in general, and propose that a series of positive feedbacks keep them active in the near surface. These include differential sediment loading and compaction, weak fault zone materials, high fluid pressure, low elastic stiffness in surrounding materials, and low confining pressure.

New molten salt systems for high-temperature molten salt batteries: LiF-LiCl-LiBr-based quaternary systems

NASA Astrophysics Data System (ADS)

Fujiwara, Syozo; Inaba, Minoru; Tasaka, Akimasa

To develop novel multi-component molten salt systems more effectively, we developed a simulative technique using the CALPHAD (Calculation of Phase Diagram and Thermodynamics) method to estimate the ionic conductivity and the melting point. The validity of this new simulative technique was confirmed by comparing the simulated ionic conductivities and melting points of typical high-temperature molten salts, such as LiF-LiCl-LiBr, LiF-LiBr-KBr, LiCl-LiBr-KBr, and LiCl-LiBr-LiI, with those reported data in the literature or experimentally obtained. This simulative technique was used to develop new quaternary molten salt systems for use as electrolytes in high-temperature molten salt batteries (called thermal batteries). The targets of the ionic conductivity and the melting point were set at 2.0 S cm -1 and higher at 500 °C, and in the range of 350-430 °C, respectively, to replace the LiCl-KCl system (1.85 S cm -1 at 500 °C) within the conventional design of the heat generation system for thermal batteries. Using the simulative method, six kinds of novel quaternary systems, LiF-LiCl-LiBr-MX (M = Na and K; X = F, Cl, and Br), which contain neither environmentally instable anions such as iodides nor expensive cations such as Rb + and Cs +, were proposed. Experimental results showed that the LiF-LiCl-LiBr-0.10NaX (X = Cl and Br) and LiF-LiCl-LiBr-0.10KX (X = F, Cl, and Br) systems meet our targets of both the ionic conductivity and the melting point.

Gravitational salt tectonics above a rising basement plateau offshore Algeria

NASA Astrophysics Data System (ADS)

Gaullier, Virginie; Vendeville, Bruno C.; Besème, Grégoire; Legoux, Gaetan; Déverchère, Jacques; Lymer, Gaël

2017-04-01

Seismic data (survey "MARADJA 1", 2003) offshore the Algerian coast have imaged an unexpected deformation pattern of the Messinian salt (Mobile Unit; MU) and its sedimentary overburden (Messinian Upper Unit and Plio-Quaternary) above an actively rising plateau in the subsalt basement. From a geodynamic point of view, the region is undergoing crustal convergence, as attested by the Boumerdes earthquake (2003, magnitude 6.8). The rise of this plateau, forming a 3D promontory restricted to the area offshore Algiers, is associated with that geodynamic setting. The seismic profiles show several subsalt thrusts (Domzig et al. 2006). The data provided additional information on the deformation of the Messinian mobile evaporitic unit and its Plio-Quaternary overburden. Margin-perpendicular profiles show mostly compressional features (anticlines and synclines) that had little activity during Messinian times, then grew more during Plio-Quaternary times. A few normal faults are also present, but are not accompanied by salt rise. By contrast, margin-parallel profiles clearly show that extensional, reactive salt diapiric ridges (symptomatic with their triangular shape in cross section) formed early, as early as the time of deposition of the Messinian Upper Unit, as recorded by fan-shaped strata. These ridges have recorded E-W, thin-skinned gravity gliding above the Messinian salt, as a response to the rise of the basement plateau. We tested this hypothesis using two analogue models, one where we assumed that the rise of the plateau started after Messinian times (initially tabular salt across the entire region), the second model assumed that the plateau had already risen partially as the Messininan Mobile Unit was deposited (salt initially thinner above the plateau than in the adjacent regions). In both experiments, the rise of the plateau generated preferential E-W extension above the salt, combined with N-S shortening. Extension was caused by gravity gliding of the salt from above the rising basement toward the deeper adjacent basins. So far, the deformation pattern of the salt and overburden on the plateau did not allow us to use it as a clear indicator of whether the plateau's rise started before or during Messinian times.

The critical relation between chemical stability of cations and water in anion exchange membrane fuel cells environment

NASA Astrophysics Data System (ADS)

Dekel, Dario R.; Willdorf, Sapir; Ash, Uri; Amar, Michal; Pusara, Srdjan; Dhara, Shubhendu; Srebnik, Simcha; Diesendruck, Charles E.

2018-01-01

Anion exchange membrane fuel cells can potentially revolutionize energy storage and delivery; however, their commercial development is hampered by a significant technological impedance: the chemical decomposition of the anion exchange membranes during operation. The hydroxide anions, while transported from the cathode to the anode, attack the positively charged functional groups in the polymer membrane, neutralizing it and suppressing its anion-conducting capability. In recent years, several new quaternary ammonium salts have been proposed to address this challenge, but while they perform well in ex-situ chemical studies, their performance is very limited in real fuel cell studies. Here, we use experimental work, corroborated by molecular dynamics modeling to show that water concentration in the environment of the hydroxide anion, as well as temperature, significantly impact its reactivity. We compare different quaternary ammonium salts that have been previously studied and test their stabilities in the presence of relatively low hydroxide concentration in the presence of different amounts of solvating water molecules, as well as different temperatures. Remarkably, with the right amount of water and at low enough temperatures, even quaternary ammonium salts which are considered "unstable", present significantly improved lifetime.

Synthesis of Quaternary Ammonium Salts of Tricyclic Cationic Drugs: A One-Pot Synthesis for the Bioorganic Chemistry Laboratory

ERIC Educational Resources Information Center

Brunauer, Linda S.; Mogannam, Abid C.; Hwee, Won B.; Chen, James Y.

2007-01-01

A one-pot conversion of tricyclic cationic drugs to their quaternary ammonium forms is described for a widely used bioactive drug: chlorpromazine, a phenothiazine-based antipsychotic. After conversion to its free base, the parent drug was methylated using substoichiometric amounts of methyl iodide dissolved in ether; the charged quaternary…

Complexes of carboxyl-containing polymer and monosubstituted bipyridinium salts

NASA Astrophysics Data System (ADS)

Merekalova, N. D.; Bondarenko, G. N.; Krylsky, D. W.; Zakirov, M. I.; Talroze, R. V.

2013-09-01

Semi-empirical PM3 method for the quantum calculations of molecular electronic structure based on NDDO integral approximation is used to investigate the complex formation of monosubstituted 4,4‧-bipyridinium salts BpyR (Hal) containing a halide anion interacting with the quaternary nitrogen atom and carboxylic group of the two-units construct. Significant effect of the BpyR (Hal) electronic structure is unveiled that contributes in two different structures of these salts, namely, partial charge transfer complex and ion pair structure, both having stable energy minima. We demonstrate that (i) the structure of the N-substituent modulates the energy and electronic characteristics of monosubstituted salts BpyR with chlorine and bromine anions and (ii) the coulomb interactions between quaternary N-atom, halogen anion, and the proton of carboxylic group stimulate the transformation of the charge transfer complex into the ion pair structure. Results of calculations are compared with the experimental FTIR spectra of blends of BpyR(Hal) with Eudragit copolymer.

Conductivity relaxation and charge transport of trihexyl tetradecyl phosphonium dicyanamide ionic liquid by broadband dielectric spectroscopy

NASA Astrophysics Data System (ADS)

Thasneema K., K.; Thayyil, M. Shahin; Krishna Kumar N., S.; Govindaraj, G.; Saheer, V. C.

2018-04-01

Usually ionic liquids consists of a large organic cation with low symmetry such as imidazolium, pyridinium, quaternary ammonium or phosponium etc combined with enormously wide range of inorganic or organic symmetric anion with melting point below 100. Ionic liquids existing in an extremely large number of possible ion pair combinations. It offers a very wide range of thermo physical properties led to the concept of designer solvents for specific applications. Due to the features of high chemical and thermal stability, low vapor pressure non flammability high ionic conductivity, and they show a good solvent ability towards a great variety of organic or inorganic compounds, ionic liquids have a widespread use in many areas such as batteries, fuel cell, solar cells, super capacitors etc. The main focus of this work is the study of molecular dynamics and conductivity relaxation of amorphous Trihexyl tetradecyl phosphonium dicyanamide ([P14,6,6,6][N(CN)2]) ionic liquid which is proved as a better electrolyte in super capacitors, over a wide frequency 10-2 Hz to 107 Hz and the temperature range between 123k and 265 k by means of Broadband Dielectric Spectroscopy. We observe alpha conductivity relaxation and secondary relaxation above and below Glass Transition Temperature. The experimental results were analyzed using electric modulus representation. The analysis emphasis the inter molecular interaction and the nature of glass forming system, whether it is fragile or strong system. The ionic liquid shows a fragile behavior and the fragility index m=123.59. TGA result of the sample exhibit a good resistance to thermal decomposition, up to 300°C.

Antibacterial surface design - Contact kill

NASA Astrophysics Data System (ADS)

Kaur, Rajbir; Liu, Song

2016-08-01

Designing antibacterial surfaces has become extremely important to minimize Healthcare Associated Infections which are a major cause of mortality worldwide. A previous biocide-releasing approach is based on leaching of encapsulated biocides such as silver and triclosan which exerts negative impacts on the environment and potentially contributes to the development of bacterial resistance. This drawback of leachable compounds led to the shift of interest towards a more sustainable and environmentally friendly approach: contact-killing surfaces. Biocides that can be bound onto surfaces to give the substrates contact-active antibacterial activity include quaternary ammonium compounds (QACs), quaternary phosphoniums (QPs), carbon nanotubes, antibacterial peptides, and N-chloramines. Among the above, QACs and N-chloramines are the most researched contact-active biocides. We review the engineering of contact-active surfaces using QACs or N-chloramines, the modes of actions as well as the test methods. The charge-density threshold of cationic surfaces for desired antibacterial efficacy and attempts to combine various biocides for the generation of new contact-active surfaces are discussed in detail. Surface positive charge density is identified as a key parameter to define antibacterial efficacy. We expect that this research field will continue to attract more research interest in view of the potential impact of self-disinfective surfaces on healthcare-associated infections, food safety and corrosion/fouling resistance required on industrial surfaces such as oil pipes and ship hulls.

Climatic, geomorphic, and archaeological implications of a late Quaternary alluvial chronology for the lower Salt River, Arizona, USA

NASA Astrophysics Data System (ADS)

Huckleberry, Gary; Onken, Jill; Graves, William M.; Wegener, Robert

2013-03-01

Recent archaeological excavations along the lower Salt River, Arizona resulted in the unexpected discovery of buried late Pleistocene soils and cultural features dating 5800-7100 cal YBP (Early Archaic), the latter representing the earliest evidence of human activity in the lower Salt River floodplain thus far identified. Because the lower Salt River floodplain has been heavily impacted by recent agriculture and urbanization and contains few stratigraphic exposures, our understanding of the river's geological history is limited. Here we present a late Quaternary alluvial chronology for a segment of the lower Salt River based on 19 accelerator mass spectrometry 14C and four optically stimulated luminescence ages obtained during two previous geoarchaeological investigations. Deposits are organized into allostratigraphic units and reveal a buried late Pleistocene terrace inset into middle-to-late Pleistocene terrace deposits. Holocene terrace fill deposits unconformably cap the late Pleistocene terrace tread in the site area, and the lower portion of this fill contains the Early Archaic archaeological features. Channel entrenchment and widening ~ 900 cal YBP eroded much of the older terrace deposits, leaving only a remnant of fill containing the buried latest Pleistocene and middle-to-late Holocene deposits preserved in the site area. Subsequent overbank deposition and channel filling associated with a braided channel system resulted in the burial of the site by a thin layer of flood sediments. Our study confirms that the lower Salt River is a complex mosaic of late Quaternary alluvium formed through vertical and lateral accretion, with isolated patches of buried soils preserved through channel avulsion. Although channel avulsion is linked to changes in sediment load and discharge and may have climatic linkages, intrinsic geomorphic and local base level controls limit direct correlations of lower Salt River stratigraphy to other large rivers in the North American Southwest.

Stille coupling via C-N bond cleavage

NASA Astrophysics Data System (ADS)

Wang, Dong-Yu; Kawahata, Masatoshi; Yang, Ze-Kun; Miyamoto, Kazunori; Komagawa, Shinsuke; Yamaguchi, Kentaro; Wang, Chao; Uchiyama, Masanobu

2016-09-01

Cross-coupling is a fundamental reaction in the synthesis of functional molecules, and has been widely applied, for example, to phenols, anilines, alcohols, amines and their derivatives. Here we report the Ni-catalysed Stille cross-coupling reaction of quaternary ammonium salts via C-N bond cleavage. Aryl/alkyl-trimethylammonium salts [Ar/R-NMe3]+ react smoothly with arylstannanes in 1:1 molar ratio in the presence of a catalytic amount of commercially available Ni(cod)2 and imidazole ligand together with 3.0 equivalents of CsF, affording the corresponding biaryl with broad functional group compatibility. The reaction pathway, including C-N bond cleavage step, is proposed based on the experimental and computational findings, as well as isolation and single-crystal X-ray diffraction analysis of Ni-containing intermediates. This reaction should be widely applicable for transformation of amines/quaternary ammonium salts into multi-aromatics.

Distribution and metabolism of quaternary amines in salt marshes

NASA Technical Reports Server (NTRS)

King, Gary M.

1985-01-01

Quaternary amines such as glycine betaine (GBT) are common osmotically active solutes in much of the marine biota. GBT is accumulated by various bacteria, algae, higher plants, invertebrates, and vertebrates in response to salinity or water stresses; in some species, GBT occurs at tens to hundreds of millimolar concentrations and can account for a significant fraction of total nitrogen. Initial studies suggest that GBT is readily converted to two potential methane precursors, trimethylamine (TMA) and acetate, in anoxic sediments. TMA is apparently the most important methane precursor in surface sediments containing sulfate reducing bacteria. In salt marshes, the bulk of the methane formed may be due to the metabolism of TMA rather than other substrates. Current research is focussed on testing this hypothesis and on determining the role of quaternary amino osmoregulatory solutes in methane fluxes from marine environments. Preliminary studies have dealt with several problems: (1) determination of GBT concentrations in the dominant flora and fauna of salt marshes; (2) synthesis of radiolabelled GBT for metabolic studies; and (3) determination of fates of BGT in marine sediments using radiotracers. Both GC and HPLC techniques have been used to assay GBT concentrations in plant and animal tissues. S. alterniflora is probably the only significant source of GBT (and indirectly of methane) since the biomass and distribution of most other species is limited. Current estimates suggest that S. alterniflora GBT could account for most of the methane efflux from salt marshes.

Thermoresponsive Poly(Ionic Liquid)s in Aqueous Salt Solutions: Salting-Out Effect on Their Phase Behavior and Water Absorption/Desorption Properties.

PubMed

Okafuji, Akiyoshi; Kohno, Yuki; Ohno, Hiroyuki

2016-07-01

Here, a thermoresponsive phase behavior of polymerized ionic liquids (PILs) composed of poly([tri-n-alkyl(vinylbenzyl)phosphonium]chloride) (poly([Pnnn VB ]Cl) is reported, where n (the number of carbon atoms of an alkyl chain) = 4, 5, or 6 after mixing with aqueous sodium chloride solutions. Both monomeric [P555VB ]Cl and the resulting poly([P555VB ]Cl) linear homopolymer show a lower critical solution temperature (LCST)-type phase behavior in aq. NaCl solutions. The phase transition temperature of the PIL shifts to lower value by increasing concentration of NaCl. Also the swelling degree of cross-linked poly([P555VB ]Cl) gel decreases by increasing NaCl concentration, clearly suggesting the "salting-out" effect of NaCl results in a significant dehydration of the poly([P555VB ]Cl) gel. The absorbed water in the PIL gel is desorbed by moderate heating via the LCST behavior, and the absolute absorption/desorption amount is improved by copolymerization of [P555VB ]Cl with more hydrophilic [P444VB ]Cl monomer. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Separation of aromatic carboxylic acids using quaternary ammonium salts on reversed-phase HPLC. 1. Separation behavior of aromatic carboxylic acids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kawamura, K.; Okuwaki, A.; Verheyen, T.

In order to develop separation processes and analytical methods for aromatic carboxylic acids for the coal oxidation products, the separation behavior of aromatic carboxylic acids on a reversed-phase HPLC using eluent containing quaternary ammonium salt has been investigated. The retention mechanism of aromatic carboxylic acids was discussed on the basis of both ion-pair partition model and ion-exchange model. The retention behavior of aromatic carboxylic acids possessing one (or two) carboxylic acid group(s) followed the ion-pair partition model, where linear free energy relationship was observed between the capacity factor and the extraction equilibrium constants of benzoic acid and naphthalene carboxylic acid.more » Besides, the retention behavior followed ion-exchange model with increasing the number of carboxylic acids, where the capacity factor of benzene polycarboxylic acids is proportional to the association constants between aromatic acids and quaternary ammonium ions calculated on the basis of an electrostatic interaction model.« less

An experimental and theoretical study of reaction mechanisms between nitriles and hydroxylamine.

PubMed

Vörös, Attila; Mucsi, Zoltán; Baán, Zoltán; Timári, Géza; Hermecz, István; Mizsey, Péter; Finta, Zoltán

2014-10-28

The industrially relevant reaction between nitriles and hydroxylamine yielding amidoximes was studied in different molecular solvents and in ionic liquids. In industry, this procedure is carried out on the ton scale in alcohol solutions and the above transformation produces a significant amount of unexpected amide by-product, depending on the nature of the nitrile, which can cause further analytical and purification issues. Although there were earlier attempts to propose mechanisms for this transformation, the real reaction pathway is still under discussion. A new detailed reaction mechanistic explanation, based on theoretical and experimental proof, is given to augment the former mechanisms, which allowed us to find a more efficient, side-product free procedure. Interpreting the theoretical results obtained, it was shown that the application of specific imidazolium, phosphonium and quaternary ammonium based ionic liquids could decrease simultaneously the reaction time while eliminating the amide side-product, leading to the targeted product selectively. This robust and economic procedure now affords a fast, selective amide free synthesis of amidoximes.

Quaternary geology and geologic hazards of the West Desert Hazardous Industry Area, Tooele County, Utah

USGS Publications Warehouse

Solomon, Barry J.; Black, Bill D.; ,

1990-01-01

The study of Quaternary geology provides information to evaluate geologic conditions and identify geologic constraints on construction in the West Desert Hazardous Industry Area (WDHIA). The WDHIA includes portions of the Great Salt Lake Desert to the west, underlain by several thousand feet of sediments capped by saline mudflats, and Ripple Valley to the east, separated from the Desert by the Grayback Hills and underlain by several hundred feet of sediments in the Cedar Mountains piedmont zone. Quaternary surficial units include marginal, shore-zone, and deep-water lacustrine sediments deposited in Pleistocene Lake Bonneville; eolian deposits; and alluvial sediments. The level of Lake Bonneville underwent major oscillations resulting in the creation of four basin-wide shorelines, three of which are recognized in the WDHIA. Geologic hazards in the WDHIA include the possible contamination of ground water in basin-fill aquifers, debris flows and flash floods in the piedmont zone, and earthquakes and related hazards. Numerous factors contribute to unsafe foundation conditions. Silty and sandy sediments may be subject to liquefaction or hydrocompaction, clayey sediments and mud flats of the Great Salt Lake Desert may be subject to shrinking or swelling, and gypsiferous dunes and salt flats are subject to subsidence due to dissolution.

HDPE/Chitosan Blends Modified with Organobentonite Synthesized with Quaternary Ammonium Salt Impregnated Chitosan

PubMed Central

de Araújo, Maria José G.; Barbosa, Rossemberg C.; Fook, Marcus Vinícius L.; Canedo, Eduardo L.; Silva, Suédina M. L.; Medeiros, Eliton S.; Leite, Itamara F.

2018-01-01

In this study, blends based on a high density polyethylene (HDPE) and chitosan (CS) were successfully prepared by melt processing, in a laboratory internal mixer. The CS biopolymer content effect (up to maximum of 40%), and, the addition of bentonite clay modified with quaternary ammonium salt (CTAB) impregnated chitosan as a compatibilizing agent, on the properties of the blends was analyzed by Fourier transform-infrared spectroscopy (FT-IR), wide angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), thermogravimetric analyses (TG), tensile strength, and scanning electron microscopy (SEM). The use of clay modified with CTAB impregnated chitosan, employing a method developed here, improved the compatibility of HDPE with chitosan, and therefore the thermal and some of the mechanical properties were enhanced, making HDPE/chitosan blends suitable candidates for food packaging. It was possible to obtain products of synthetic polymer, HDPE, with natural polymer, chitosan, using a method very used industrially, with acceptable and more friendly properties to the environment, when compared to conventional synthetic polymers. In addition, due to the possibility of impregnated chitosan with quaternary ammonium salt exhibit higher antibacterial activity than neat chitosan, the HDPE/chitosan/organobentonite blends may be potentially applied in food containers to favor the preservation of food for a longer time in comparison to conventional materials. PMID:29438286

HDPE/Chitosan Blends Modified with Organobentonite Synthesized with Quaternary Ammonium Salt Impregnated Chitosan.

PubMed

de Araújo, Maria José G; Barbosa, Rossemberg C; Fook, Marcus Vinícius L; Canedo, Eduardo L; Silva, Suédina M L; Medeiros, Eliton S; Leite, Itamara F

2018-02-13

In this study, blends based on a high density polyethylene (HDPE) and chitosan (CS) were successfully prepared by melt processing, in a laboratory internal mixer. The CS biopolymer content effect (up to maximum of 40%), and, the addition of bentonite clay modified with quaternary ammonium salt (CTAB) impregnated chitosan as a compatibilizing agent, on the properties of the blends was analyzed by Fourier transform-infrared spectroscopy (FT-IR), wide angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), thermogravimetric analyses (TG), tensile strength, and scanning electron microscopy (SEM). The use of clay modified with CTAB impregnated chitosan, employing a method developed here, improved the compatibility of HDPE with chitosan, and therefore the thermal and some of the mechanical properties were enhanced, making HDPE/chitosan blends suitable candidates for food packaging. It was possible to obtain products of synthetic polymer, HDPE, with natural polymer, chitosan, using a method very used industrially, with acceptable and more friendly properties to the environment, when compared to conventional synthetic polymers. In addition, due to the possibility of impregnated chitosan with quaternary ammonium salt exhibit higher antibacterial activity than neat chitosan, the HDPE/chitosan/organobentonite blends may be potentially applied in food containers to favor the preservation of food for a longer time in comparison to conventional materials.

Flocculation and antimicrobial properties of a cationized starch.

PubMed

Liu, Zhouzhou; Huang, Mu; Li, Aimin; Yang, Hu

2017-08-01

In this study, a series of cationized starch-based flocculants (starch-3-chloro-2-hydroxypropyl triethyl ammonium chloride, St-CTA) containing various quaternary ammonium salt groups on the starch backbone were prepared using a simple etherification reaction. All of the prepared starch-based flocculants show effective performance for the flocculation of kaolin suspension, two bacterial (Escherichia coli and Staphylococcus aureus) suspensions, and two contaminant mixtures (kaolin and each bacterium) under most pH conditions. St-CTA with a high substitution degree of CTA demonstrates improved contaminant removal efficiency because of the strong cationic nature of the grafted quaternary ammonium salt groups and the charge naturalization flocculation effect. The antibacterial effects of St-CTA were also evaluated, considering that many quaternary ammonium salt compounds elicit bactericidal effects. Three-dimensional excitation-emission matrix spectra and direct cell morphological observation under scanning electron microscopy reveal that the starch-based flocculants exhibit better antibacterial effects on the Gram-negative bacterium E. coli than on the Gram-positive bacterium S. aureus. The thicker cell wall due to the presence of abundant peptidoglycan and teichoic acids of S. aureus than E. coli explains the uneasy breakage of S. aureus cell wall after being attacked by the cationized starch-based flocculants. Copyright © 2017 Elsevier Ltd. All rights reserved.

[The action of quaternary ammonium derivatives on respiration and nitrate reduction in Pseudomonas aeruginosa].

PubMed

Bievskiĭ, A N

1994-01-01

It was revealed that the same dosages of quaternary ammonium derivatives, such as decamethoxin and cetyltrimethylammonium bromide, inhibited the respiratory chains and caused destruction of Pseudomonas aeruginosa under aerobic conditions more effectively than under anaerobic ones when anions of nitric acid were the terminal acceptors of electrons. It was also registered that Pseudomonas were able to dissimilatory nitrate reduction in the media under the polysaccharide layer that was produced by these bacteria: this fact possibly proves the possibility of survival of denitrifying bacteria in solutions with high concentrations of quaternary ammonium salts. The data obtained permit supposing that inhibitors of respiratory chains and oxidizers may be used as potentiators of the antimicrobial action of quaternary ammonium derivatives.

SEPARATION OF INORGANIC SALTS FROM ORGANIC SOLUTIONS

DOEpatents

Katzin, L.I.; Sullivan, J.C.

1958-06-24

A process is described for recovering the nitrates of uranium and plutonium from solution in oxygen-containing organic solvents such as ketones or ethers. The solution of such salts dissolved in an oxygen-containing organic compound is contacted with an ion exchange resin whereby sorption of the entire salt on the resin takes place and then the salt-depleted liquid and the resin are separated from each other. The reaction seems to be based on an anion formation of the entire salt by complexing with the anion of the resin. Strong base or quaternary ammonium type resins can be used successfully in this process.

Low Temperature Double-Layer Capacitors Using Asymmetric and Spiro-Type Quaternary Ammonium Salts

NASA Technical Reports Server (NTRS)

Smart, Marshall C. (Inventor); Brandon, Erik J. (Inventor); West, William C. (Inventor)

2014-01-01

Double-layer capacitors capable of operating at extremely low temperatures (e.g., as low as -80.degree. C.) are disclosed. Electrolyte solutions combining a base solvent (e.g., acetonitrile) and a cosolvent are employed to lower the melting point of the base electrolyte. Example cosolvents include methyl formate, ethyl acetate, methyl acetate, propionitrile, butyronitrile, and 1,3-dioxolane. A quaternary ammonium salt including at least one of triethylmethylammonium tetrafluoroborate (TEMATFB) and spiro-(1,1')-bipyrrolidium tetrafluoroborate (SBPBF.sub.4), is used in an optimized concentration (e.g., 0.10 M to 0.75 M), dissolved into the electrolyte solution. Conventional device form factors and structural elements (e.g., porous carbon electrodes and a polyethylene separator) may be employed.

Ionic liquids composed of phosphonium cations and organophosphate, carboxylate, and sulfonate as lubricant antiwear additives

DOE PAGES

Zhou, Yan; Dyck, Jeffrey; Graham, Todd; ...

2014-10-20

Oil-soluble phosphonium-based ionic liquids (ILs) have recently been reported as potential ashless lubricant additives. This study is to expand the IL chemistry envelope and to achieve fundamental correlations between the ion structures and ILs’ physiochemical and tribological properties. Here we present eight ILs containing two different phosphonium cations and seven different anions from three groups: organophosphate, carboxylate, and sulfonate. The oil solubility of ILs seems largely governed by the IL molecule size and structure complexity. When used as oil additives, the ranking of effectiveness in wear protection for the anions are: organophosphate > carboxylate > sulfonate. All selected ILs outperformedmore » a commercial ashless anti-wear additive. Surface characterization from the top and the cross-section revealed the nanostructures and compositions of the tribo-films formed by the ILs. Some fundamental insights were achieved: branched and long alkyls improve the IL’s oil solubility, anions of a phosphonium-phosphate IL contribute most phosphorus in the tribofilm, and carboxylate anions, though free of P, S, N, or halogen, can promote the formation of an anti-wear tribofilm.« less

Formation and shape-control of hierarchical cobalt nanostructures using quaternary ammonium salts in aqueous media

PubMed Central

Deshmukh, Ruchi; Mehra, Anurag

2017-01-01

Aggregation and self-assembly are influenced by molecular interactions. With precise control of molecular interactions, in this study, a wide range of nanostructures ranging from zero-dimensional nanospheres to hierarchical nanoplates and spindles have been successfully synthesized at ambient temperature in aqueous solution. The nanostructures reported here are formed by aggregation of spherical seed particles (monomers) in presence of quaternary ammonium salts. Hydroxide ions and a magnetic moment of the monomers are essential to induce shape anisotropy in the nanostructures. The cobalt nanoplates are studied in detail, and a growth mechanism based on collision, aggregation, and crystal consolidation is proposed based on a electron microscopy studies. The growth mechanism is generalized for rods, spindles, and nearly spherical nanostructures, obtained by varying the cation group in the quaternary ammonium hydroxides. Electron diffraction shows different predominant lattice planes on the edge and on the surface of a nanoplate. The study explains, hereto unaddressed, the temporal evolution of complex magnetic nanostructures. These ferromagnetic nanostructures represent an interesting combination of shape anisotropy and magnetic characteristics. PMID:28326240

Extraction Selectivity of a Quaternary Alkylammonium Salt for Trivalent Actinides over Trivalent Lanthanides: Does Extractant Aggregation Play a Role?

DOE PAGES

Knight, Andrew W.; Chiarizia, Renato; Soderholm, L.

2017-05-10

In this paper, the extraction behavior of a quaternary alkylammonium salt extractant was investigated for its selectivity for trivalent actinides over trivalent lanthanides in nitrate and thiocyanate media. The selectivity was evaluated by solvent extraction experiments through radiochemical analysis of 241Am and 152/154Eu. Solvent extraction distribution and slope-analysis experiments were performed with americium(III) and europium(III) with respect to the ligand (nitrate and thiocyanate), extractant, and metal (europium only) concentrations. Further evaluation of the equilibrium expression that governs the extraction process indicated the appropriate use of the saturation method for estimation of the aggregation state of quaternary ammonium extractants in themore » organic phase. From the saturation method, we observed an average aggregation number of 5.4 ± 0.8 and 8.5 ± 0.9 monomers/aggregate for nitrate and thiocyanate, respectively. Through a side-by-side comparison of the nitrate and thiocyanate forms, we discuss the potential role of the aggregation in the increased selectivity for trivalent actinides over trivalent lanthanides in thiocyanate media.« less

Extraction Selectivity of a Quaternary Alkylammonium Salt for Trivalent Actinides over Trivalent Lanthanides: Does Extractant Aggregation Play a Role?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Knight, Andrew W.; Chiarizia, Renato; Soderholm, L.

In this paper, the extraction behavior of a quaternary alkylammonium salt extractant was investigated for its selectivity for trivalent actinides over trivalent lanthanides in nitrate and thiocyanate media. The selectivity was evaluated by solvent extraction experiments through radiochemical analysis of 241Am and 152/154Eu. Solvent extraction distribution and slope-analysis experiments were performed with americium(III) and europium(III) with respect to the ligand (nitrate and thiocyanate), extractant, and metal (europium only) concentrations. Further evaluation of the equilibrium expression that governs the extraction process indicated the appropriate use of the saturation method for estimation of the aggregation state of quaternary ammonium extractants in themore » organic phase. From the saturation method, we observed an average aggregation number of 5.4 ± 0.8 and 8.5 ± 0.9 monomers/aggregate for nitrate and thiocyanate, respectively. Through a side-by-side comparison of the nitrate and thiocyanate forms, we discuss the potential role of the aggregation in the increased selectivity for trivalent actinides over trivalent lanthanides in thiocyanate media.« less

Phase diagram of the LiNO3-NaNO3-NaCl-Sr(NO3)2 salt system

NASA Astrophysics Data System (ADS)

Rasulov, A. I.; Gasanaliev, A. M.; Mamedova, A. K.; Gamataeva, B. Yu.

2015-04-01

The phase diagram of the quaternary LiNO3-NaNO3-NaCl-Sr(NO3)2 system is studied by means of differential thermal analysis, and the compositions and crystallization temperatures of nonvariant equilibrium phases are revealed. The temperature dependence of conductivity in eutectic and peritectic salt compositions is investigated.

Map showing thickness of saturated Quaternary deposits, Sugar House quadrangle, Salt Lake County, Utah, February 1972

USGS Publications Warehouse

Mower, R.W.

1973-01-01

Saturated Quaternary deposits in the Sugar Horse quadrangle supply significant quantities of water to wells from which water is withdrawn for domestic, municipal, industrial, and irrigation uses. The deposits consist of clay, silt, sand, and gravel; individual beds range from a few inches to several tens of feet thick. The principal aquifer, which is almost completely within the Quaternary deposits, supplied about 4 percent, or 9,000 acre-feet, of the municipal and industrial water used annually in Salt Lake County during 1964-68.As a general rule, more water is stored and more water will be yielded to a well where aquifers are thicker. This map can be used as a general guide to those areas where greatest amounts of water are stored in the aquifer, and where yields to wells may be greater. Local variations in the ability of saturated deposits to transmit water can alter the general relationship between aquifer thickness and yield of wells.The thickness of saturated Quaternary deposits within the area of the Sugar Horse quadrangle ranges from zero to about 650 feet, as shown on the map. The thickest section of these deposits is near the southwestern corner of the quadrangle, and the thinnest section is along the mountain front adjacent to the approximate eastern limit of saturated Quaternary deposits.The thickness of saturated Quaternary deposits shown on this map is based on drillers’ logs for 55 deep wells (which show the thickness of the Quaternary deposits) and on water-level measurements made in February 1972 in wells in unconfined shallow aquifers.Reports in the following list of selected references contain other information about the saturated Quaternary deposits in this and adjacent parts of Jordan Valley, Utah. The basic-data reports and releases contain well logs, water-level measurements, and other types of basic ground-water data. The interpretive repots contain discussions of the occurrence of ground water, tests to determine hydraulic properties of the aquifer, and related information. Ground-water terms used in this report have been defined by Lohman and others (1972).

Highly stable noble-metal nanoparticles in tetraalkylphosphonium ionic liquids for in situ catalysis.

PubMed

Banerjee, Abhinandan; Theron, Robin; Scott, Robert W J

2012-01-09

Gold and palladium nanoparticles were prepared by lithium borohydride reduction of the metal salt precursors in tetraalkylphosphonium halide ionic liquids in the absence of any organic solvents or external nanoparticle stabilizers. These colloidal suspensions remained stable and showed no nanoparticle agglomeration over many months. A combination of electrostatic interactions between the coordinatively unsaturated metal nanoparticle surface and the ionic-liquid anions, bolstered by steric protection offered by the bulky alkylated phosphonium cations, is likely to be the reason behind such stabilization. The halide anion strongly absorbs to the nanoparticle surface, leading to exceptional nanoparticle stability in halide ionic liquids; other tetraalkylphosphonium ionic liquids with non-coordinating anions, such as tosylate and hexafluorophosphate, show considerably lower affinities towards the stabilization of nanoparticles. Palladium nanoparticles stabilized in the tetraalkylphosphonium halide ionic liquid were stable, efficient, and recyclable catalysts for a variety of hydrogenation reactions at ambient pressures with sustained activity. Aerial oxidation of the metal nanoparticles occurred over time and was readily reversed by re-reduction of oxidized metal salts. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molten salts in Nuclear Reactors (Bibliography); LES SELS FONDUS DANS LES REACTEURS NUCLEAIRES (BIBLIOGRAPHIE)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dirian, J.; Saint-James, R.

1959-01-01

A collection is presented of references dealing with the physicochemical studies of fused salts, in partictular the alkali and alkali earth halides. Numerous binary, ternary and quaternary systems of these halides with those of uranium and thoriuna are examined, and the physical properties, density, viscosity, and vapor pressure going from the halides to the mixtures are also considered. References relating to the corrosion of materials by these salts are included and the treatment of the salts with a view to recovery after irradiation in a nuclear reactor is discussed. (auth)

Generation of Perfluoroalkyl Acids from Aerobic Biotransformation of Quaternary Ammonium Polyfluoroalkyl Surfactants.

PubMed

Mejia-Avendaño, Sandra; Vo Duy, Sung; Sauvé, Sébastien; Liu, Jinxia

2016-09-20

The aerobic biotransformation over 180 days of two cationic quaternary ammonium compounds (QACs) with perfluoroalkyl chains was determined in soil microcosms, and biotransformation pathways were proposed. This is the first time that polyfluoroalkyl cationic surfactants used in aqueous film-forming foam (AFFF) formulations were studied for their environmental fate. The biotransformation of perfluorooctaneamido quaternary ammonium salt (PFOAAmS) was characterized by a DT50 value (time necessary to consume half of the initial mass) of 142 days and significant generation of perfluoroalkyl carboxylic acid (PFOA) at a yield of 30 mol % by day 180. The biotransformation of perfluorooctane sulfonamide quaternary ammonium salt (PFOSAmS) was very slow with unobservable change of the spiked mass; yet the generation of perfluorooctanesulfonate (PFOS) at a yield of 0.3 mol % confirmed the biotransformation of PFOSAmS. Three novel biotransformation intermediates were identified for PFOAAmS and three products including perfluorooctane sulfonamide (FOSA) for PFOSAmS through high-resolution mass spectrometry (MS) analysis and t-MS(2) fragmentation. The significantly slower PFOSAmS biotransformation is hypothesized to be due to its stronger sorption to soil owing to a longer perfluoroalkyl chain and a bulkier sulfonyl group, when compared to PFOAAmS. This study has demonstrated that despite overall high stability of QACs and their biocide nature, the ones with perfluoroalkyl chains can be substantially biotransformed into perfluoroalkyl acids in aerobic soil.

Determination of the distribution constants of aromatic compounds and steroids in biphasic micellar phosphonium ionic liquid/aqueous buffer systems by capillary electrokinetic chromatography.

PubMed

Lokajová, Jana; Railila, Annika; King, Alistair W T; Wiedmer, Susanne K

2013-09-20

The distribution constants of some analytes, closely connected to the petrochemical industry, between an aqueous phase and a phosphonium ionic liquid phase, were determined by ionic liquid micellar electrokinetic chromatography (MEKC). The phosphonium ionic liquids studied were the water-soluble tributyl(tetradecyl)phosphonium with chloride or acetate as the counter ion. The retention factors were calculated and used for determination of the distribution constants. For calculating the retention factors the electrophoretic mobilities of the ionic liquids were required, thus, we adopted the iterative process, based on a homologous series of alkyl benzoates. Calculation of the distribution constants required information on the phase-ratio of the systems. For this the critical micelle concentrations (CMC) of the ionic liquids were needed. The CMCs were calculated using a method based on PeakMaster simulations, using the electrophoretic mobilities of system peaks. The resulting distribution constants for the neutral analytes between the ionic liquid and the aqueous (buffer) phase were compared with octanol-water partitioning coefficients. The results indicate that there are other factors affecting the distribution of analytes between phases, than just simple hydrophobic interactions. Copyright © 2013 Elsevier B.V. All rights reserved.

Thermally-responsive, nonflammable phosphonium ionic liquid electrolytes for lithium metal batteries: operating at 100 degrees celsius.

PubMed

Lin, X; Kavian, R; Lu, Y; Hu, Q; Shao-Horn, Y; Grinstaff, M W

2015-11-13

Rechargeable batteries such as Li ion/Li metal batteries are widely used in the electronics market but the chemical instability of the electrolyte limits their use in more demanding environmental conditions such as in automotive, oil exploration, or mining applications. In this study, a series of alkyl phosphonium ionic liquid electrolyte are described with high thermal stability and solubility for LiTFSI. A lithium metal battery (LMB) containing a tailored phosphonium ionic liquid/LiTFSI electrolyte operates at 100 °C with good specific capacities and cycling stability. Substantial capacity is maintained during 70 cycles or 30 days. Instant on-off battery operation is realized via the significant temperature dependence of the electrolyte material, demonstrating the robustness and potential for use at high temperature.

[Dental plaque microcosm biofilm behavior on a resin composite incorporated with nano-antibacterial inorganic filler containing long-chain alkyl quaternary ammonium salt].

PubMed

Junling, Wu; Qiang, Zhang; Ruinan, Sun; Ting, Zhu; Jianhua, Ge; Chuanjian, Zhou

2015-12-01

To develop a resin composite incorporated with nano-antibacterial inorganic filler containing long-chain alkyl quaternary ammonium salt, and to measure its effect on human dental plaque microcosm biofilm. A novel nano-antibacterial inorganic filler containing long-chain alkyl quaternary ammonium salt was synthesized according to methods introduced in previous research. Samples of the novel nano-antibacterial inorganic fillers were modified by a coupling agent and then added into resin composite at 0%, 5%, 10%, 15% or 20% mass fractions; 0% composite was used as control. A flexural test was used to measure resin composite mechanical properties. Results showed that a dental plaque microcosm biofilm model with human saliva as inoculum was formed. Colony-forming unit (CFU) counts, lactic acid production, and live/dead assay of biofilm on the resin composite were calculated to test the effect of the resin composite on human dental plaque microcosm biofilm. The incorporation of nano-antibacterial inorganic fillers with as much as 15% concentration into the resin composite showed no adverse effect on the mechanical properties of the resin composite (P > 0.05). Resin composite containing 5% or more nano-antibacterial inorganic fillers significantly inhibited the metabolic activity of dental plaque microcosm biofilm, suggesting its strong antibacterial potency (P < 0.05). This novel resin composite exhibited a strong antibacterial property upon the addition of up to 5% nano-antibacterial inorganic fillers, thereby leading to effective caries inhibition in dental application.

Sensitive electrospray mass spectrometry analysis of one-bead-one-compound peptide libraries labeled by quaternary ammonium salts.

PubMed

Bąchor, Remigiusz; Cydzik, Marzena; Rudowska, Magdalena; Kluczyk, Alicja; Stefanowicz, Piotr; Szewczuk, Zbigniew

2012-08-01

A rapid and straightforward method for high-throughput analysis of single resin beads from one-bead-one-compound combinatorial libraries with high resolution electrospray ionization tandem mass spectrometry (HR ESI-MS/MS) is presented. The application of an efficient method of peptide derivatization by quaternary ammonium salts (QAS) formation increases ionization efficiency and reduces the detection limit, allowing analysis of trace amounts of compounds by ESI-MS. Peptides, synthesized on solid support, contain a new cleavable linker composed of a Peg spacer (9-aza-3,6,12,15-tetraoxa-10-on-heptadecanoic acid), lysine with ɛ-amino group marked by the N,N,N-triethylglycine salt, and methionine, which makes possible the selective cleavage by cyanogen bromide. Even a small portion of peptides derivatized by QAS cleaved from a single resin bead is sufficient for sequencing by HR ESI-MS/MS experiments. The developed strategy was applied to a small training library of α chymotrypsin substrates. The obtained results confirm the applicability of the proposed method in combinatorial chemistry.

Effects of phosphonium-based ionic liquids on phospholipid membranes studied by small-angle X-ray scattering.

PubMed

Kontro, Inkeri; Svedström, Kirsi; Duša, Filip; Ahvenainen, Patrik; Ruokonen, Suvi-Katriina; Witos, Joanna; Wiedmer, Susanne K

2016-12-01

The effects of ionic liquids on model phospholipid membranes were studied by small-angle X-ray scattering, dynamic light scattering (DLS) and zeta potential measurements. Multilamellar 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine liposomes and large unilamellar vesicles composed of l-α-phosphatidylcholine (eggPC) and l-α-phosphatidylglycerol (eggPG) (80:20mol%) or eggPC, eggPG, and cholesterol (60:20:20mol%) were used as biomimicking membrane models. The effects of the phosphonium-based ionic liquids: tributylmethylphosphonium acetate, trioctylmethylphosphonium acetate, tributyl(tetradecyl)-phosphonium acetate, and tributyl(tetradecyl)-phosphonium chloride, were compared to those of 1-ethyl-3-methyl-imidazolium acetate. With multilamellar vesicles, the ionic liquids that did not disrupt liposomes decreased the lamellar spacing as a function of concentration. The magnitude of the effect depended on concentration for all studied ionic liquids. Using large unilamellar vesicles, first a slight decrease in the vesicle size, then aggregation of vesicles was observed by DLS for increasing ionic liquid concentrations. At concentrations just below those that caused aggregation of liposomes, large unilamellar vesicles were coated by ionic liquid cations, evidenced by a change in their zeta potential. The ability of phosphonium-based ionic liquids to affect liposomes is related to the length of the hydrocarbon chains in the cation. Generally, the ability of ionic liquids to disrupt liposomes goes hand in hand with inducing disorder in the phospholipid membrane. However, trioctylmethylphosphonium acetate selectively extracted and induced a well-ordered lamellar structure in phospholipids from disrupted cholesterol-containing large unilamellar vesicles. This kind of effect was not seen with any other combination of ionic liquids and liposomes. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Interaction between crustal tectonics and salt deformation in the Eastern Sardinian margin, Western Tyrrhenian Sea: seismic data and analogue modelling

NASA Astrophysics Data System (ADS)

Vendeville, Bruno; Lymer, Gael; Gaullier, Virginie; Chanier, Frank; Maillard, Agnes; Sage, Françoise; Lofi, Johanna; Thinon, Isabelle

2014-05-01

The Tyrrhenian Basin opened by eastward migration of the Apennine subduction system. Rifting along the Eastern Sardinian margin started during the middle to late Miocene times and hence this timing partly overlapped the Messinian Salinity Crisis. The two "METYSS" cruises were conducted to use the deformation of the Messinian salt and its Plio-Quaternary overburden as a proxy for better delineating the tectonic history of the sub-salt basement. Many parts of the study area contain two of the most typical Messinian series of the Western Mediterranean: the Mobile Unit (MU; salt, mainly halite), overlain by the more competent Upper Unit (UU: alternating dolomitic marls and anhydrite). The brittle Plio-Quaternary cover overlies the UU. Usually, the presence of mobile salt is viewed as a nuisance for understanding crustal tectonics because salt's ability to act as a structural buffer between the basement and the cover. However, we illustrate, using examples from the Cornaglia Terrace, how we can use thin-skinned salt tectonics as indicators of vertical movements in the sub-salt, pre-Messinian basement. There, slip along N-S-trending crustal normal faults bounding basement troughs has been recorded by salt and overburden in two different manners: - First, post-salt basement faulting (typically after deposition of the Upper Unit and the early Pliocene), and some crustal-scale southward tilting, triggered along-strike (southward) thin-skinned, gliding of salt and overburden recorded by upslope extension and downslope shortening. - Second, and less obvious at first glance, there was some crustal activity along another basement trough, located East of the Baronie Ridge after deposition of the Messinian salt. This trough is narrow, trends N-S and is bounded by crustal faults. The narrow width of the trough allowed for only minor across-strike (E-W) gliding. The resulting geometry would suggest that nothing happened after Messinian times, but some structural features (confirmed by analogue modelling) show that basement fault slip and tilting (Eastward or Westward) was accommodated by lateral flow of salt, which thinned upslope and inflated downslope, while the overlying sediments remained sub-horizontal.

Synergistic Effects Between Phosphonium-Alkylphosphate Ionic Liquids and Zinc Dialkyldithiophosphate (ZDDP) as Lubricant Additives

DOE PAGES

Qu, Jun; Barnhill, William C.; Luo, Huimin; ...

2015-07-14

Unique synergistic effects between phosphonium-alkylphosphate ionic liquids and zinc dialkyldithiophosphate (ZDDP) are discovered when used together as lubricant additives, resulting in significant friction and wear reduction along with distinct tribofilm composition and mechanical properties. The synergism is attributed to the 30-70× higher-than-nominal concentrations of hypothetical new compounds (via anion exchange between IL and ZDDP) on the fluid surface/interface.

Disinfection of Water with Quaternary Ammonium Salts Insolubilized on a Porous Glass Surface

PubMed Central

Nakagawa, Yoshihiro; Hayashi, Hiroyuki; Tawaratani, Takahiko; Kourai, Hiroki; Horie, Tokunaru; Shibasaki, Isao

1984-01-01

Insoluble quaternary ammonium salts bound to porous glass showed antibacterial activity. An agent designated as G12, which had a dodecyl alkyl chain, was selected for some antibacterial tests on comparison of it with the agent reported previously. The antibacterial activity of G12 toward Escherichia coli was mainly due to the adsorption of cells and therefore gradually decreased during continuous treatment of a cell suspension. The lost G12 activity was completely recovered by washing with ethanol, and the activity of refreshed G12 decreased in the same manner as that of fresh G12. The lost activity was, however, always recovered only by ethanol treatment. This indicated that G12 might interact with cells more strongly by means of a hydrophobic force than an electrostatic one. The antimicrobial spectrum showed that G12 was effective against not only bacteria but also yeasts. PMID:16346491

Quaternary ammonium salt N-(dodecyloxycarboxymethyl)-N,N,N-trimethyl ammonium chloride induced alterations in Saccharomyces cerevisiae physiology.

PubMed

Oblak, Ewa; Piecuch, Agata; Maciaszczyk-Dziubinska, Ewa; Wawrzycka, Donata

2016-12-01

We investigated the influence of the quaternary ammonium salt (QAS) called IM (N-(dodecyloxycarboxymethyl)- N,N,N-trimethyl ammonium chloride) on yeast cells of the parental strain and the IM-resistant mutant (EO25 IMR) growth. The phenotype of this mutant was pleiotropic. The IMR mutant exhibited resistance to ethanol, osmotic shock and oxidative stress, as well as increased sensitivity to UV. Moreover, it was noted that mutant EO25 appears to have an increased resistance to clotrimazole, ketoconazole, fluconazole, nystatin and cycloheximide. It also tolerated growth in the presence of crystal violet, DTT and metals (selenium, tin, arsenic). It was shown that the presence of IM decreased ergosterol level in mutant plasma membrane and increased its unsaturation. These results indicate changes in the cell lipid composition. Western blot analysis showed the induction of Pma1 level by IM. RT-PCR revealed an increased PMA1 expression after IM treatment.

Quaternary isoquinoline alkaloids from Xylopia parviflora.

PubMed

Nishiyama, Yumi; Moriyasu, Masataka; Ichimaru, Momoyo; Iwasa, Kinuko; Kato, Atsushi; Mathenge, Simon G; Chalo Mutiso, Patrick B; Juma, Francis D

2004-04-01

From the quaternary alkaloidal fraction of the bark and the root of Xylopia parviflora (Annonaceae), four isoquinoline alkaloids, xylopinidine, dehydrocoreximine, N, N-dimethylanomurine and N-methylphoebine were isolated along with the known compounds, pycnarrhine, lotusine, 6,7-dimethoxy-2-methyl-isoquinolinium salt, 1,2-dehydroreticuline, (-)-phellodendrine, (+)-tembetarine, (-)-litcubine, (+)-magnoflorine, tetradehydroreticuline, (-)-oblongine, (+)-menisperine, (+)-N-methylcorydine, stepharanine, (+)-xanthoplanine, dehydrodiscretine, jatrorrhizine and palmatine. 3,4-Dihydro-6,7-dimethoxy-2-methyl-isoquinolinium and N-methylpurpuerine were isolated as natural products for the first time. Their structures were determined on the basis of spectroscopic evidence.

Antibacterial activities of fluorescent nano assembled triphenylamine phosphonium ionic liquids.

PubMed

Brunel, Frédéric; Lautard, Christelle; Garzino, Frédéric; Giorgio, Suzanne; Raimundo, Jean M; Bolla, Jean M; Camplo, Michel

2016-08-01

Staphylococcus aureus, a Gram positive coccal bacterium is a major cause of nosocomial infection. We report the synthesis of new triphenylamine phosphonium ionic liquids which are able to self-assemble into multiwall nanoassemblies and to reveal a strong bactericidal activity (MIC=0.5mg/L) for Gram positive bacteria (including resistant strains) comparable to that of standard antibiotics. Time kill, metabolism and fluorescence confocal microscopy studies show a quasi-instantaneously penetration of the nanoassemblies inside the bacteria resulting of a rapid blocking (30min) of their proliferation. As confirmed by rezasurin reduction monitoring, these compounds strongly affect the bacterial metabolism and a Gram positive versus Gram negative selectivity is clearly observed. These fluorescent phosphonium ionic liquid might constitute a useful tool for both translocation studies and to tackle infectious diseases related to the field of implantology. Copyright © 2016 Elsevier Ltd. All rights reserved.

Turbulence and Cavitation Suppression by Quaternary Ammonium Salt Additives.

PubMed

Naseri, Homa; Trickett, Kieran; Mitroglou, Nicholas; Karathanassis, Ioannis; Koukouvinis, Phoevos; Gavaises, Manolis; Barbour, Robert; Diamond, Dale; Rogers, Sarah E; Santini, Maurizio; Wang, Jin

2018-05-16

We identify the physical mechanism through which newly developed quaternary ammonium salt (QAS) deposit control additives (DCAs) affect the rheological properties of cavitating turbulent flows, resulting in an increase in the volumetric efficiency of clean injectors fuelled with diesel or biodiesel fuels. Quaternary ammonium surfactants with appropriate counterions can be very effective in reducing the turbulent drag in aqueous solutions, however, less is known about the effect of such surfactants in oil-based solvents or in cavitating flow conditions. Small-angle neutron scattering (SANS) investigations show that in traditional DCA fuel compositions only reverse spherical micelles form, whereas reverse cylindrical micelles are detected by blending the fuel with the QAS additive. Moreover, experiments utilising X-ray micro computed tomography (micro-CT) in nozzle replicas, quantify that in cavitation regions the liquid fraction is increased in the presence of the QAS additive. Furthermore, high-flux X-ray phase contrast imaging (XPCI) measurements identify a flow stabilization effect in the region of vortex cavitation by the QAS additive. The effect of the formation of cylindrical micelles is reproduced with computational fluid dynamics (CFD) simulations by including viscoelastic characteristics for the flow. It is demonstrated that viscoelasticity can reduce turbulence and suppress cavitation, and subsequently increase the injector's volumetric efficiency.

Quaternary ammonium-functionalized MCM-48 mesoporous silica as a sorbent for the dispersive solid-phase extraction of endocrine disrupting compounds in water.

PubMed

Zhang, Shijuan; Lu, Fengli; Ma, Xiaoyun; Yue, Mingbo; Li, Yanxin; Liu, Jiammin; You, Jinmao

2018-07-06

MCM-48 mesoporous silica was functionalized with dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, a quaternary ammonium salt with a long hydrophobic chain, to prepare a new sorbent for the dispersive solid-phase extraction (DSPE) of seven endocrine disrupting compounds (EDCs) including 4-hexylphenol, 4-octylphenol, 4-nonylphenol, bisphenol A, estrone, 17β-estradiol and estriol in water. A series of differently functionalized MCM-48 materials were also synthesized, and they served as reference materials to study the mechanism. The developed DSPE method was combined with HPLC with fluorescence detection to evaluate the adsorption performance. The results indicated that the quaternary ammonium-functionalized MCM-48 mesoporous silica can be used as ideal sorbent for EDCs in water with recoveries of higher than 95% due to the electrostatic interactions and hydrophobic effect. Hydrogen bonding and π-π interactions in other synthesized materials could lead to about 25-30% increase in recoveries, but the results for polyhydroxy compounds were still not satisfying. The quaternary ammonium-functionalized MCM-48 mesoporous silica was successfully applied to the DSPE of EDCs in real water samples. The optimum extraction conditions were sorbent amount, 15 mg; desorption time; 5 min; elution volume, 0.8 mL; sample pH 3.0; and salt addition, 5 g/L. The limits of detection were in the range of 1.2-2.6 ng/L, while the limits of quantitation were in the range of 4.3-8.3 ng/L. Copyright © 2018 Elsevier B.V. All rights reserved.

Tested Demonstrations.

ERIC Educational Resources Information Center

Gilbert, George L., Ed.

1980-01-01

Two demonstrations are described: (1) a variant of preparing purple benzene by phase transfer catalysis with quaternary ammonium salts and potassium permanganate in which crown ethers are used; (2) a corridor or "hallway" demonstration in which unknown molecular models are displayed and prizes awarded to students correctly identifying the…

Functionalization of graphene using deep eutectic solvents

NASA Astrophysics Data System (ADS)

Hayyan, Maan; Abo-Hamad, Ali; AlSaadi, Mohammed AbdulHakim; Hashim, Mohd Ali

2015-08-01

Deep eutectic solvents (DESs) have received attention in various applications because of their distinctive properties. In this work, DESs were used as functionalizing agents for graphene due to their potential to introduce new functional groups and cause other surface modifications. Eighteen different types of ammonium- and phosphonium-salt-based DESs were prepared and characterized by FTIR. The graphene was characterized by FTIR, STA, Raman spectroscopy, XRD, SEM, and TEM. Additional experiments were performed to study the dispersion behavior of the functionalized graphene in different solvents. The DESs exhibited both reduction and functionalization effects on DES-treated graphene. Dispersion stability was investigated and then characterized by UV-vis spectroscopy and zeta potential. DES-modified graphene can be used in many applications, such as drug delivery, wastewater treatment, catalysts, composite materials, nanofluids, and biosensors. To the best of our knowledge, this is the first investigation on the use of DESs for graphene functionalization.

Functionalization of graphene using deep eutectic solvents.

PubMed

Hayyan, Maan; Abo-Hamad, Ali; AlSaadi, Mohammed AbdulHakim; Hashim, Mohd Ali

2015-12-01

Deep eutectic solvents (DESs) have received attention in various applications because of their distinctive properties. In this work, DESs were used as functionalizing agents for graphene due to their potential to introduce new functional groups and cause other surface modifications. Eighteen different types of ammonium- and phosphonium-salt-based DESs were prepared and characterized by FTIR. The graphene was characterized by FTIR, STA, Raman spectroscopy, XRD, SEM, and TEM. Additional experiments were performed to study the dispersion behavior of the functionalized graphene in different solvents. The DESs exhibited both reduction and functionalization effects on DES-treated graphene. Dispersion stability was investigated and then characterized by UV-vis spectroscopy and zeta potential. DES-modified graphene can be used in many applications, such as drug delivery, wastewater treatment, catalysts, composite materials, nanofluids, and biosensors. To the best of our knowledge, this is the first investigation on the use of DESs for graphene functionalization.

Tuning the dispersion of multiwall carbon nanotubes in co-continuous polymer blends: a generic approach

NASA Astrophysics Data System (ADS)

Bose, Suryasarathi; Bhattacharyya, Arup R.; Khare, Rupesh A.; Kulkarni, Ajit R.; Umasankar Patro, T.; Sivaraman, P.

2008-08-01

Melt-mixed blends of polyamide 6 and acrylonitrile-butadiene-styrene (PA6/ABS) with multiwall carbon nanotubes (MWNTs) were prepared with the intention to develop conducting composites. A generic strategy, namely specific interactions combined with reactive coupling, was adopted to facilitate and to retain the 'network-like' structure of MWNTs during melt-mixing. This was facilitated by the sodium salt of 6-amino hexanoic acid (Na-AHA) and certain phosphonium based modifiers, where it was envisaged that these modifiers would establish specific interactions (either 'cation-π' or 'π-π' ) with the 'π-electron' clouds of MWNTs, as well as restricting them in the PA6 phase of the blends via reactive coupling. This route eventually led to a remarkable increase in the electrical conductivity and dielectric constant in the blends with MWNTs. Raman, FTIR and TEM investigations further supported these observations.

Reversible electro-optic device employing aprotic molten salts and method

DOEpatents

Warner, Benjamin P [Los Alamos, NM; McCleskey, T Mark [Los Alamos, NM; Burrell, Anthony K [Los Alamos, NM; Hall, Simon B [Palmerston North, NZ

2008-01-08

A single-compartment reversible mirror device having a solution of aprotic molten salt, at least one soluble metal-containing species comprising metal capable of being electrodeposited, and at least one anodic compound capable of being oxidized was prepared. The aprotic molten salt is liquid at room temperature and includes lithium and/or quaternary ammonium cations, and anions selected from trifluoromethylsulfonate (CF.sub.3SO.sub.3.sup.-), bis(trifluoromethylsulfonyl)imide ((CF.sub.3SO.sub.2).sub.2N.sup.-), bis(perfluoroethylsulfonyl)imide ((CF.sub.3CF.sub.2SO.sub.2).sub.2N.sup.-) and tris(trifluoromethylsulfonyl)methide ((CF.sub.3SO.sub.2).sub.3C.sup.-). A method for preparing substantially pure molten salts is also described.

Reversible Electro-Optic Device Employing Aprotic Molten Salts And Method

DOEpatents

Warner, Benjamin P.; McCleskey, T. Mark; Burrell, Anthony K.; Hall, Simon B.

2005-03-01

A single-compartment reversible mirror device having a solution of aprotic molten salt, at least one soluble metal-containing species comprising metal capable of being electrodeposited, and at least one anodic compound capable of being oxidized was prepared. The aprotic molten salt is liquid at room temperature and includes lithium and/or quaternary ammonium cations, and anions selected from trifluoromethylsulfonate (CF.sub.3 SO.sub.3.sup.-), bis(trifluoromethylsulfonyl)imide ((CF.sub.3 SO.sub.2).sub.2 N.sup.-), bis(perfluoroethylsulfonyl)imide ((CF.sub.3 CF.sub.2 SO.sub.2).sub.2 N.sup.-) and tris(trifluoromethylsulfonyl)methide ((CF.sub.3 SO.sub.2).sub.3 C.sup.-). A method for preparing substantially pure molten salts is also described.

Gauze Impregnated With Quaternary Ammonium Salt Reduces Bacterial Colonization of Surgical Drains After Breast Reconstruction.

PubMed

Strong, Amy L; Wolfe, Emily T; Shank, Nina; Chaffin, Abigail E; Jansen, David A

2018-06-01

Surgical site infection after breast reconstruction is associated with increased length of hospital stay, readmission rates, cost, morbidity, and mortality. Identifying methods to reduce surgical site infection without the use of antibiotics may be beneficial at reducing antimicrobial resistance, reserving the use of antibiotics for more severe cases. Quaternary ammonium salts have previously been shown to be a safe and effective antimicrobial agent in the setting of in vitro and in vivo animal experiments. A retrospective study was conducted to investigate the antimicrobial properties of a quaternary ammonium salt, 3-trimethoxysilyl propyldimethyloctadecyl ammonium chloride (QAS-3PAC; Bio-spear), at reducing surgical drain site colonization and infection after breast reconstruction (deep inferior epigastric perforator flap reconstruction or tissue expander placement). Twenty patients were enrolled, with 14 surgical drains covered with nonimpregnated gauze and 17 surgical drains covered with QAS-3PAC impregnated gauze, for the purposes of investigating bacterial colonization. Antibiotic sensitivity analysis was also conducted when bacterial cultures were positive. The overall incidence of bacterial colonization of surgical drains was lower in the treatment group compared with the control group (17.6% vs 64.3%, respectively; P = 0.008). QAS-3PAC impregnated gauze reduced the incidence of bacterial colonization of surgical drains during the first (0.0% vs 33.3%) and second (33.3% vs 87.5%; P = 0.04) postoperative week. Furthermore, no enhanced antibiotic resistance was noted on drains treated with QAS-3PAC impregnated gauze. The results of this study suggest that QAS-3PAC impregnated gauze applied over surgical drains may be an effective method for reducing the incidence of bacterial colonization.

Drilling fluid containing a copolymer filtration control agent

DOE Office of Scientific and Technical Information (OSTI.GOV)

Enright, D.P.; Lucas, J.M.; Perricone, A.C.

1981-10-06

The invention relates to an aqueous drilling fluid composition, a filtration control agent for utilization in said aqueous drilling fluid, and a method of forming a filter cake on the wall of a well for the reduction of filtrate from said drilling fluid, by utilization of a copolymer of: (1) a (Meth) acrylamido alkyl sulfonic acid or alkali metal salt thereof; and (2) a (Meth) acrylamide or n-alkyl (Meth) acrylamide. The copolymer may be cross-linked with a quaternary ammonium salt cross-linking agent.

Peroxotantalate-Based Ionic Liquid Catalyzed Epoxidation of Allylic Alcohols with Hydrogen Peroxide.

PubMed

Ma, Wenbao; Chen, Chen; Kong, Kang; Dong, Qifeng; Li, Kun; Yuan, Mingming; Li, Difan; Hou, Zhenshan

2017-05-29

The efficient and environmentally benign epoxidation of allylic alcohols has been attained by using new kinds of monomeric peroxotantalate anion-functionalized ionic liquids (ILs=[P 4,4,4,n ] 3 [Ta(O) 3 (η-O 2 )], P 4,4,4,n =quaternary phosphonium cation, n=4, 8, and 14), which have been developed and their structures determined accordingly. This work revealed the parent anions of the ILs underwent structural transformation in the presence of H 2 O 2 . The formed active species exhibited excellent catalytic activity, with a turnover frequency for [P 4,4,4,4 ] 3 [Ta(O) 3 (η-O 2 )] of up to 285 h -1 , and satisfactory recyclability in the epoxidation of various allylic alcohols under very mild conditions by using only one equivalent of hydrogen peroxide as an oxidant. NMR studies showed the reaction was facilitated through a hydrogen-bonding mechanism, in which the peroxo group (O-O) of the peroxotantalate anion served as the hydrogen-bond acceptor and hydroxyl group in the allylic alcohols served as the hydrogen-bond donor. This work demonstrates that simple monomeric peroxotantalates can catalyze epoxidation of allylic alcohols efficiently. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Separation of the isomers of benzene poly(carboxylic acid)s by quaternary ammonium salt via formation of deep eutectic solvents.

PubMed

Hou, Yucui; Li, Jian; Ren, Shuhang; Niu, Muge; Wu, Weize

2014-11-26

Because of similar properties and very low volatility, isomers of benzene poly(carboxylic acid)s (BPCAs) are very difficult to separate. In this work, we found that isomers of BPCAs could be separated efficiently by quaternary ammonium salts (QASs) via formation of deep eutectic solvents (DESs). Three kinds of QASs were used to separate the isomers of BPCAs, including the isomers of benzene tricarboxylic acids (trimellitic acid, trimesic acid, and hemimellitic acid) and the isomers of benzene dicarboxylic acids (phthalic acid and isophthalic acid). Among the QASs, tetraethylammonium chloride was found to have the best performance, which could completely separate BPCA isomers in methyl ethyl ketone solutions. It was found that the hydrogen bond forming between QAS and BPCA results in the selective separation of BPCA isomers. QAS in DES was regenerated effectively by the antisolvent method, and the regenerated QAS was reused four times with the same high efficiency.

Investigation of melamine derived quaternary as ammonium salt potential shale inhibitor

NASA Astrophysics Data System (ADS)

Yu, Hongjiang; Hu, Weimin; Guo, Gang; Huang, Lei; Li, Lili; Gu, Xuefan; Zhang, Zhifang; Zhang, Jie; Chen, Gang

2017-06-01

Melamine, sodium chloroacetate and sodium hydroxide were used as raw materials to synthesize a kind of neutral quaternary ammonium salt (NQAS) as potential clay swelling inhibitor and water-based drilling fluid additive, and the reaction conditions were screened based on the linear expansion rate of bentonite. The inhibitive properties of NQASs were investigated by various methods, including montmorillonite (MMT) linear expansion test, mud ball immersing test, particle distribution measurement, thermogravimetric analysis and scanning electron microscopy etc. The results indicate that NQAS can inhibit expansion and dispersion of clay in water effectively. At the same condition, the bentonite linear expansion rate in NQAS-6 solution is much lower than those of others, and the hydration expansion degree of the mud ball in 0.5% NQAS-6 solution is appreciably weaker than the control test. The compatibility test indicates NQAS-6 could be compatible with the conventional additives in water-based drilling fluids, and the temperature resistance of modified starch was improved effectively. Meanwhile, the inhibitive mechanism was discussed through the particle distribution measurement.

Effect of Quaternary Ammonium Salts with Fluorine Atoms on Selected Weed Species.

PubMed

Biczak, Robert; Pawłowska, Barbara; Płatkowski, Maciej; Stręk, Michał; Telesiński, Arkadiusz

2017-04-01

This study investigated the effects of four structurally different quaternary ammonium salts (QASs), i.e., tetrabutylammonium tetrafluoroborate [TBA][BF 4 ], tetrahexylammonium tetrafluoroborate [THA][BF 4 ], tetrabutylammonium hexafluorophosphate [TBA][PF 6 ], and tetrahexylammonium hexafluorophosphate [THA][PF 6 ], on the growth and development of three weed species: gallant soldier (Galinsoga parviflora Cav.), white goosefoot (Chenopodium album L.) and common sorrel (Rumex acetosa L.). The examined compounds were applied in the form of foliar spraying and soil application. Strong herbicidal properties of the examined compounds were demonstrated in case of their soil application. Growth inhibition of plant shoots and roots was greater with soil application than with foliar treatment. The strongest herbicidal activity of compounds was demonstrated with [TBA][BF 4 ] have demonstrated [TBA][BF 4 ] and [TBA][PF 6 ] applied to the soil, while [THA][BF 4 ] demonstrated the weakest herbicidal action. The increased concentration of applied QASs caused a decrease in the assimilation pigments, change in dry weight content and inhibition of length of shoots and roots.

A Novel Water-soluble Ratiometric Fluorescent Probe Based on FRET for Sensing Lysosomal pH.

PubMed

Song, Guang-Jie; Bai, Su-Yun; Luo, Jing; Cao, Xiao-Qun; Zhao, Bao-Xiang

2016-11-01

A new ratiometric fluorescent probe based on Förster resonance energy transfer (FRET) for sensing lysosomal pH has been developed. The probe (RMPM) was composed of imidazo[1,5-α]pyridine quaternary ammonium salt fluorophore as the FRET donor and the rhodamine moiety as the FRET acceptor. It's the first time to report that imidazo[1,5-α]pyridine quaternary ammonium salt acts as the FRET donor. The ratio of fluorescence intensity of the probe at two wavelengths (I 424 /I 581 ) changed significantly and responded linearly toward minor pH changes in the range of 5.4-6.6. It should be noted that it's rare to report that a ratiometric pH probe could detect so weak acidic pH with pKa = 6.31. In addition, probe RMPM exhibited excellent water-solubility, fast-response, all-right selectivity and brilliant reversibility. Moreover, RMPM has been successfully applied to sensing lysosomal pH in HeLa cells and has low cytotoxicity.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Yan; Dyck, Jeffrey; Graham, Todd

Oil-soluble phosphonium-based ionic liquids (ILs) have recently been reported as potential ashless lubricant additives. This study is to expand the IL chemistry envelope and to achieve fundamental correlations between the ion structures and ILs’ physiochemical and tribological properties. Here we present eight ILs containing two different phosphonium cations and seven different anions from three groups: organophosphate, carboxylate, and sulfonate. The oil solubility of ILs seems largely governed by the IL molecule size and structure complexity. When used as oil additives, the ranking of effectiveness in wear protection for the anions are: organophosphate > carboxylate > sulfonate. All selected ILs outperformedmore » a commercial ashless anti-wear additive. Surface characterization from the top and the cross-section revealed the nanostructures and compositions of the tribo-films formed by the ILs. Some fundamental insights were achieved: branched and long alkyls improve the IL’s oil solubility, anions of a phosphonium-phosphate IL contribute most phosphorus in the tribofilm, and carboxylate anions, though free of P, S, N, or halogen, can promote the formation of an anti-wear tribofilm.« less

Thermally-responsive, nonflammable phosphonium ionic liquid electrolytes for lithium metal batteries: operating at 100 degrees celsius† †Electronic supplementary information (ESI) available: Detailed ionic liquids synthesis, characterization, conductivity, cyclic voltammetry, battery cycling and those of other compositions; SEM images; energy density calculation. See DOI: 10.1039/c5sc01518a Click here for additional data file.

PubMed Central

Lin, X.; Kavian, R.; Lu, Y.; Hu, Q.; Shao-Horn, Y.

2015-01-01

Rechargeable batteries such as Li ion/Li metal batteries are widely used in the electronics market but the chemical instability of the electrolyte limits their use in more demanding environmental conditions such as in automotive, oil exploration, or mining applications. In this study, a series of alkyl phosphonium ionic liquid electrolyte are described with high thermal stability and solubility for LiTFSI. A lithium metal battery (LMB) containing a tailored phosphonium ionic liquid/LiTFSI electrolyte operates at 100 °C with good specific capacities and cycling stability. Substantial capacity is maintained during 70 cycles or 30 days. Instant on-off battery operation is realized via the significant temperature dependence of the electrolyte material, demonstrating the robustness and potential for use at high temperature. PMID:28757963

Understanding the impact of the central atom on the ionic liquid behavior: phosphonium vs ammonium cations.

PubMed

Carvalho, Pedro J; Ventura, Sónia P M; Batista, Marta L S; Schröder, Bernd; Gonçalves, Fernando; Esperança, José; Mutelet, Fabrice; Coutinho, João A P

2014-02-14

The influence of the cation's central atom in the behavior of pairs of ammonium- and phosphonium-based ionic liquids was investigated through the measurement of densities, viscosities, melting temperatures, activity coefficients at infinite dilution, refractive indices, and toxicity against Vibrio fischeri. All the properties investigated are affected by the cation's central atom nature, with ammonium-based ionic liquids presenting higher densities, viscosities, melting temperatures, and enthalpies. Activity coefficients at infinite dilution show the ammonium-based ionic liquids to present slightly higher infinite dilution activity coefficients for non-polar solvents, becoming slightly lower for polar solvents, suggesting that the ammonium-based ionic liquids present somewhat higher polarities. In good agreement these compounds present lower toxicities than the phosphonium congeners. To explain this behavior quantum chemical gas phase DFT calculations were performed on isolated ion pairs at the BP-TZVP level of theory. Electronic density results were used to derive electrostatic potentials of the identified minimum conformers. Electrostatic potential-derived CHelpG and Natural Population Analysis charges show the P atom of the tetraalkylphosphonium-based ionic liquids cation to be more positively charged than the N atom in the tetraalkylammonium-based analogous IL cation, and a noticeable charge delocalization occurring in the tetraalkylammonium cation, when compared with the respective phosphonium congener. It is argued that this charge delocalization is responsible for the enhanced polarity observed on the ammonium based ionic liquids explaining the changes in the thermophysical properties observed.

Understanding the impact of the central atom on the ionic liquid behavior: Phosphonium vs ammonium cations

NASA Astrophysics Data System (ADS)

Carvalho, Pedro J.; Ventura, Sónia P. M.; Batista, Marta L. S.; Schröder, Bernd; Gonçalves, Fernando; Esperança, José; Mutelet, Fabrice; Coutinho, João A. P.

2014-02-01

The influence of the cation's central atom in the behavior of pairs of ammonium- and phosphonium-based ionic liquids was investigated through the measurement of densities, viscosities, melting temperatures, activity coefficients at infinite dilution, refractive indices, and toxicity against Vibrio fischeri. All the properties investigated are affected by the cation's central atom nature, with ammonium-based ionic liquids presenting higher densities, viscosities, melting temperatures, and enthalpies. Activity coefficients at infinite dilution show the ammonium-based ionic liquids to present slightly higher infinite dilution activity coefficients for non-polar solvents, becoming slightly lower for polar solvents, suggesting that the ammonium-based ionic liquids present somewhat higher polarities. In good agreement these compounds present lower toxicities than the phosphonium congeners. To explain this behavior quantum chemical gas phase DFT calculations were performed on isolated ion pairs at the BP-TZVP level of theory. Electronic density results were used to derive electrostatic potentials of the identified minimum conformers. Electrostatic potential-derived CHelpG and Natural Population Analysis charges show the P atom of the tetraalkylphosphonium-based ionic liquids cation to be more positively charged than the N atom in the tetraalkylammonium-based analogous IL cation, and a noticeable charge delocalization occurring in the tetraalkylammonium cation, when compared with the respective phosphonium congener. It is argued that this charge delocalization is responsible for the enhanced polarity observed on the ammonium based ionic liquids explaining the changes in the thermophysical properties observed.

Salt diapirs in the Dead Sea basin and their relationship to Quaternary extensional tectonics

USGS Publications Warehouse

Al-Zoubi, A.; ten Brink, Uri S.

2001-01-01

Regional extension of a brittle overburden and underlying salt causes differential loading that is thought to initiate the rise of reactive diapirs below and through regions of thin overburden. We present a modern example of a large salt diapir in the Dead Sea pull-apart basin, the Lisan diapir, which we believe was formed during the Quaternary due to basin transtension and subsidence. Using newly released seismic data that are correlated to several deep wells, we determine the size of the diapir to be 13 x 10 km. its maximum depth 7.2 km. and its roof 125 m below the surface. From seismic stratigraphy, we infer that the diapir started rising during the early to middle Pleistocene as this section of the basin underwater rapid subsidence and significant extension of the overburden. During the middle to late Pleistocene, the diapir pierced through the extensionally thinned overburden, as indicated by rim synclines, which attest to rapid salt withdrawal from the surrounding regions. Slight positive topography above the diapir and shallow folded horizons indicate that it is still rising intermittently. The smaller Sedom diapir, exposed along the western bounding fault of the basin is presently rising and forms a 200 m-high ridge. Its initiation is explained by localized E-W extension due monoclinal draping over the edge of a rapidly subsiding basin during the early to middle Pleistocene, and its continued rise by lateral squeezing due to continued rotation of the Amazyahu diagonal fault. 

Late quaternary geomorphology of the Great Salt Lake region, Utah, and other hydrographically closed basins in the western United States: A summary of observations

NASA Technical Reports Server (NTRS)

Currey, Donald R.

1989-01-01

Attributes of Quaternary lakes and lake basins which are often important in the environmental prehistory of semideserts are discussed. Basin-floor and basin-closure morphometry have set limits on paleolake sizes; lake morphometry and basin drainage patterns have influenced lacustrine processes; and water and sediment loads have influenced basin neotectonics. Information regarding inundated, runoff-producing, and extra-basin spatial domains is acquired directly from the paleolake record, including the littoral morphostratigraphic record, and indirectly by reconstruction. Increasingly detailed hypotheses regarding Lake Bonneville, the largest late Pleistocene paleolake in the Great Basin, are subjects for further testing and refinement. Oscillating transgression of Lake Bonneville began about 28,000 yr B.P.; the highest stage occurred about 15,000 yr B.P., and termination occurred abruptly about 13,000 yr B.P. A final resurgence of perennial lakes probably occurred in many subbasins of the Great Basin between 11,000 and 10,000 yr B.P., when the highest stage of Great Salt Lake (successor to Lake Bonneville) developed the Gilbert shoreline. The highest post-Gilbert stage of Great Salt Lake, which has been one of the few permanent lakes in the Great Basin during Holocene time, probably occurred between 3,000 and 2,000 yr B.P.

Characterization and Thermal Properties of Nitrate Based Molten Salt for Heat Recovery System

NASA Astrophysics Data System (ADS)

Faizal Tukimon, Mohd; Muhammad, Wan Nur Azrina Wan; Nor Annuar Mohamad, Md; Yusof, Farazila

2017-10-01

Molten salt can acts like a storage medium or heat transfer fluid in heat recovery system. Heat transfer fluid is a fluid that has the capability to deliver heat this one side to another while heat recovery system is a system that transfers heat to produce energy. This studies shows about determining the new formulation of different molten nitrate/nitrite salts consisting of LiNO3, KNO2, KNO3 and NaNO2 that give a low temperature of melting point and high average specific heat capacity. Mixed alkaline molten nitrate/nitrite salt can act as a heat transfer fluid due to their advantageous in terms of its properties that feasible in heat recovery system such as high specific heat capacity, low vapour pressure, low cost and wide range of temperature in its application. The mixing of these primary substances will form a new line of quaternary nitrate salt (LiNO3 - KNO2 - KNO3 - NaNO2). The quaternary mixture was heated inside the box furnace at 150°C for four hours and rose up the temperature to 400°C for eight hours to homogenize the mixture. Through heating process, the elements of nitrate/nitrite base were mixed completely. The temperature was then reduced to 115°C for several hours before removing the mixture from the furnace. The melting point of each sample were testified by using thermal gravimetric analysis, TGA/DTA and experiment of determining the specific heat capacity were conducted by using Differential Scanning Calorimeter, DSC. From the result, it is found that the melting point Sample 1 with percentage of weightage (25.4wt% of LiNO3, 33.8wt% of KNO2, 20.7wt% of KNO3 and 20.1wt% of NaNO2) is 94.4°C whereas the average specific heat capacity was 1.0484/g°C while for Sample 3 with percentages of weightage (30.0wt% of LiNO3, 50.2wt% of KNO2, 3.1wt% of KNO3 and 16.7wt% of NaNO2), the melting point is 86.1°C with average specific heat capacity of 0.7274 J/g°C. In the nut shell, the quaternary mixture salts had been a good mixture with good thermal properties that low in melting point and have high specific heat capacity which could be a potential heat transfer fluid in heat recovery application.

Cellular Membrane Phospholipids Act as a Depository for Quaternary Amine containing Drugs thus competing with the Acetylcholine / Nicotinic Receptor

PubMed Central

Barbacci, Damon; Jackson, Shelley N.; Muller, Ludovic; Egan, Thomas; Lewis, Ernest K.; Schultz, J. Albert; Woods, Amina S.

2014-01-01

We previously demonstrated that ammonium- or guanidinium- phosphate interactions are key to forming non-covalent complexes (NCXs) through salt bridge formation with G-protein coupled receptors (GPCR), which are immersed in the cell membrane's lipids. The present work highlights MALDI ion mobility coupled to orthogonal time-of-flight mass spectrometry (MALDI IM oTOF MS) as a method to determine qualitative and relative quantitative affinity of drugs to form NCXs with targeted GPCRs' epitopes in a model system using, bis-quaternary amine based drugs, α- and β- subunit epitopes of the nicotinic acetylcholine receptor' (nAChR) and phospholipids. Bis-quaternary amines proved to have a strong affinity for all nAChR epitopes and negatively charged phospholipids, even in the presence of the physiological neurotransmitter acetylcholine. Ion mobility baseline separated isobaric phosphatidyl ethanolamine and a matrix cluster, providing an accurate estimate for phospholipid counts. Overall this technique is a powerful method for screening drugs' interactions with targeted lipids and protein respectively containing quaternary amines and guanidinium moieties. PMID:22506649

Peptides derivatized with bicyclic quaternary ammonium ionization tags. Sequencing via tandem mass spectrometry.

PubMed

Setner, Bartosz; Rudowska, Magdalena; Klem, Ewelina; Cebrat, Marek; Szewczuk, Zbigniew

2014-10-01

Improving the sensitivity of detection and fragmentation of peptides to provide reliable sequencing of peptides is an important goal of mass spectrometric analysis. Peptides derivatized by bicyclic quaternary ammonium ionization tags: 1-azabicyclo[2.2.2]octane (ABCO) or 1,4-diazabicyclo[2.2.2]octane (DABCO), are characterized by an increased detection sensitivity in electrospray ionization mass spectrometry (ESI-MS) and longer retention times on the reverse-phase (RP) chromatography columns. The improvement of the detection limit was observed even for peptides dissolved in 10 mM NaCl. Collision-induced dissociation tandem mass spectrometry of quaternary ammonium salts derivatives of peptides showed dominant a- and b-type ions, allowing facile sequencing of peptides. The bicyclic ionization tags are stable in collision-induced dissociation experiments, and the resulted fragmentation pattern is not significantly influenced by either acidic or basic amino acid residues in the peptide sequence. Obtained results indicate the general usefulness of the bicyclic quaternary ammonium ionization tags for ESI-MS/MS sequencing of peptides. Copyright © 2014 John Wiley & Sons, Ltd.

Physical, chemical and antimicrobial evaluation of a composite material containing quaternary ammonium salt for braces cementation.

PubMed

Sugii, Mari Miura; Ferreira, Fábio Augusto de Souza; Müller, Karina Cogo; Lima, Debora Alves Nunes Leite; Groppo, Francisco Carlos; Imasato, Hidetake; Rodrigues-Filho, Ubirajara Pereira; Aguiar, Flávio Henrique Baggio

2017-04-01

The antibiofilm effect of iodide quaternary ammonium methacryloxy silicate (IQAMS) in Transbond XT Light Cure Adhesive resin used for braces cementation was evaluated. Fourier Transform Infrared (FTIR) spectroscopy confirmed IQAMS formation and Scanning Electron Microscopy coupled to Energy-Dispersive X-ray Spectroscopy (SEM-EDS) revealed that as coating, the quaternary ammonium groups from IQAMS were homogeneously dispersed throughout the surface. When incorporated, the composite material presented homogeneous dispersion throughout the resin. Assays with Streptococcus mutans demonstrated enhanced antibiofilm effect for the IQAMS coated resin, with much lower colony-forming units (CFU), in comparison to incorporated IQAMS. Such a difference was assigned to low availability of quaternary ammonium groups at the surface of resin when IQAMS was incorporated, hindering its antibiofilm effect. Additionally, the incorporation of IQAMS led to slight decrease in ultimate bond strength (UBS) and shear bond strength (SBS), in comparison to the neat commercial resin. Thus, the synthesized IQAMS displays great potential as antibiofilm coating or sealant to prevent oral infections in brackets during orthodontic treatment. Copyright © 2016 Elsevier B.V. All rights reserved.

USSR Report, Chemistry

DTIC Science & Technology

1984-01-06

Sep-Oct 83) ................................. ANALYTICAL CHEMISTRY Ionometric Determination of Copper in Organic Compounds S(S. L. Davydova, et al...Committee Reviews Progress in Fertilizer Industry (EKONOMICHESKAYA GAZETA, No 42, Oct 83) .................. 30 INORGANIC COMPOUNDS Speed of Ultrasound...Sep 83).. ........... .......... . . .. . . . . .... 39 NITROGEN COMPOUNDS Phototropy of Quaternary Ammonium Salts of N,N’-Bis- Substituted Diimides

3-(2-aminophenyl)-4-methyl-1,3-thiazole-2(3H)-thione as an ecofriendly sulphur transfer agent to prepare alkanethiols in high yield and high purity.

PubMed

Mehdid, Mohammed Amine; Djafri, Ayada; Roussel, Christian; Andreoli, Federico

2009-11-12

A new process is described for preparing very pure linear alkanethiols and linear alpha,omega-alkanedithiols using a sequential alkylation of the title compound, followed by a ring closure to quantitatively give the corresponding 3-methyl[1,3]thiazolo[3,2-a]-[3,1]benzimidazol-9-ium salt and the alkanethiol derivative under mild conditions. The alkanethiol and the heteroaromatic salt are easily separated by a simple extraction process. The intermediate thiazolium quaternary salts resulting from the first reaction step can be isolated in quantitative yields, affording an odourless protected form of the thiols.

Subsurface stratigraphy and geochemistry of late Quaternary evaporites, Searles Lake, California, with a section on radiocarbon ages of stratigraphic units

USGS Publications Warehouse

Smith, George I.; Stuiver, Minze

1979-01-01

Searles Lake is a dry salt pan, about 100 km 2 in area, that lies on the floor of Searles Valley, in the desert of southeast California. Several salt bodies of late Quaternary age lie beneath the surface, mostly composed of sodium and potassium carbonate, sulfate, chloride, and borate minerals. Mud layers separate the salt bodies, which contain interstitial brine that is the source of large quantities of industrial chemicals. The value of annual production from the deposit exceeds $30 million; total production to date exceeds $1 billion. The salts and muds were deposited during Pleistocene and Holocene times by a series of large lakes (200 m maximum depth, 1,000 km 2 maximum area) that fluctuated in size in response to climatic change. Salts were deposited during major dry (interpluvial) episodes, muds during wet (pluvial) episodes that correlate with glacial advances in other parts of North America and the world. Data based on cores from the deposit are used in this paper to establish the stratigraphy of the deposit, the chemical and mineral compositions of successive units, and the total quantities of components contained by them. These parameters are then used to determine the geochemical evolution of the sedimentary layers. The results provide a refined basis for reconstructing the limnology of Searles Lake and the regional climate during late Quaternary time. Six main stratigraphic units were distinguished and informally named earlier on the basis of their dominant composition: Unit Typical thickness 14C age, uncorrected (in meters) (years B.P.) Overburden Mud 7 0 to >3,500 Upper Salt 15 >3,500 to 10,500 Parting Mud 4 10,500 to 24,000 Lower Salt 12 24,000 to 32,500 Bottom Mud 30 32,500 to 130,000 Mixed Layer 200+ > 130,000 (The age of 130,000 years for the Mixed Layer is based on extrapolated sedimentation rates.) The Lower Salt is subdivided into seven salt units (S-l to S-7) and six mud units (M-2 to M-7), the Mixed Layer into six units (A to F). For each salt unit, the areal extent, volume, shape, mineralogy, and chemical composition of the solids and brines have been determined; for each mud unit (which originally extended over much of the basin), the shape and volume within a standard area, and the mineralogy, have been determined. The bulk compositions (brines plus salts) of the combined Lower Salt units S-l to S-5 and units S-6 and S-7, and the Upper Salt, were determined so that the total quantities and ratios of ions in the initial brines could be reconstructed. The 74 published HC dates on Searles Lake core samples from all but the oldest unit are supplemented by 14 new dates (determined by Minze Stuiver) on the Lower Salt. Most of the age control comes from dates based on disseminated organic carbon; two dates are on wood; dates on carbonate minerals are less reliable. Although the probable disequilibrium between the carbon in the lake and atmosphere (because of contamination, slow equilibrium rates, and other factors) causes disseminated carbon dates to be an estimated 500-2,500 years 'too old,' the ages of the major and minor units are relatively well established. The list above indicates rounded and uncorrected ages for the contacts of major units. The age of the only salt bed in the Lower Salt which indicates desiccation (S-5) is about 28,000 years. The average uncorrected sedimentation rate in the Parting Mud is 4

Leaf water relations and net gas exchange responses of salinized Carrizo citrange seedlings during drought stress and recovery.

PubMed

Pérez-Pérez, J G; Syvertsen, J P; Botía, P; García-Sánchez, F

2007-08-01

Since salinity and drought stress can occur together, an assessment was made of their interacting effects on leaf water relations, osmotic adjustment and net gas exchange in seedlings of the relatively chloride-sensitive Carrizo citrange, Citrus sinensis x Poncirus trifoliata. Plants were fertilized with nutrient solution with or without additional 100 mm NaCl (salt and no-salt treatments). After 7 d, half of the plants were drought stressed by withholding irrigation water for 10 d. Thus, there were four treatments: salinized and non-salinized plants under drought-stress or well-watered conditions. After the drought period, plants from all stressed treatments were re-watered with nutrient solution without salt for 8 d to study recovery. Leaf water relations, gas exchange parameters, chlorophyll fluorescence, proline, quaternary ammonium compounds and leaf and root concentrations of Cl(-) and Na(+) were measured. Salinity increased leaf Cl(-) and Na(+) concentrations and decreased osmotic potential (Psi(pi)) such that leaf relative water content (RWC) was maintained during drought stress. However, in non-salinized drought-stressed plants, osmotic adjustment did not occur and RWC decreased. The salinity-induced osmotic adjustment was not related to any accumulation of proline, quaternary ammonium compounds or soluble sugars. Net CO(2) assimilation rate (A(CO2)) was reduced in leaves from all stressed treatments but the mechanisms were different. In non-salinized drought-stressed plants, lower A(CO2) was related to low RWC, whereas in salinized plants decreased A(CO2) was related to high levels of leaf Cl(-) and Na(+). A(CO2) recovered after irrigation in all the treatments except in previously salinized drought-stressed leaves which had lower RWC and less chlorophyll but maintained high levels of Cl(-), Na(+) and quaternary ammonium compounds after recovery. High leaf levels of Cl(-) and Na(+) after recovery apparently came from the roots. Plants preconditioned by salinity stress maintained a better leaf water status during drought stress due to osmotic adjustment and the accumulation of Cl(-) and Na(+). However, high levels of salt ions impeded recovery of leaf water status and photosynthesis after re-irrigation with non-saline water.

Preparation and Characterization of Natural Rubber/Organophilic Clay Nanocomposites

NASA Astrophysics Data System (ADS)

Gonzales-Fernandes, M.; Esper, F. J.; Silva-Valenzuela, M. G.; Martín-Cortés, G. R.; Valenzuela-Diaz, F. R.; Wiebeck, H.

Natural rubber/organophilic clay nanocomposites were prepared and characterized. A brown bentonite from Paraiba's State, Brazil was modified with a sodium salt and treated with quaternary ammonium salt hexadecyltrimethyl ammonium chloride. The clay in its natural state, after cation exchange with sodium and after organophilization was characterized by XRD, IR, SEM, thermal analysis. Nanocomposite samples were prepared containing 10 resin percent of organophilic clay. The vulcanized samples were analyzed by XRD, SEM. The nanocomposites obtained showed improvement in their mechanical properties in comparison with samples without clay.

Ion transport and structural dynamics in homologous ammonium and phosphonium-based room temperature ionic liquids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Griffin, Philip J., E-mail: pgrif@seas.upenn.edu; Holt, Adam P.; Tsunashima, Katsuhiko

2015-02-28

Charge transport and structural dynamics in a homologous pair of ammonium and phosphonium based room temperature ionic liquids (ILs) have been characterized over a wide temperature range using broadband dielectric spectroscopy and quasi-elastic light scattering spectroscopy. We have found that the ionic conductivity of the phosphonium based IL is significantly enhanced relative to the ammonium homolog, and this increase is primarily a result of a lower glass transition temperature and higher ion mobility. Additionally, these ILs exhibit pronounced secondary relaxations which are strongly influenced by the atomic identity of the cation charge center. While the secondary relaxation in the phosphoniummore » IL has the expected Arrhenius temperature dependence characteristic of local beta relaxations, the corresponding relaxation process in the ammonium IL was found to exhibit a mildly non-Arrhenius temperature dependence in the measured temperature range—indicative of molecular cooperativity. These differences in both local and long-range molecular dynamics are a direct reflection of the subtly different inter-ionic interactions and mesoscale structures found in these homologous ILs.« less

Ion transport and structural dynamics in homologous ammonium and phosphonium-based room temperature ionic liquids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Griffin, Phillip J.; Holt, Adam P.; Tsunashima, Katsuhiko

2015-02-01

Charge transport and structural dynamics in a homologous pair of ammonium and phosphonium based room temperature ionic liquids (ILs) have been characterized over a wide temperature range using broadband dielectric spectroscopy and quasi-elastic light scattering spectroscopy. We have found that the ionic conductivity of the phosphonium based IL is significantly enhanced relative to the ammonium homolog, and this increase is primarily a result of a lower glass transition temperature and higher ion mobility. Additionally, these ILs exhibit pronounced secondary relaxations which are strongly influenced by the atomic identity of the cation charge center. While the secondary relaxation in the phosphoniummore » IL has the expected Arrhenius temperature dependence characteristic of local beta relaxations, the corresponding relaxation process in the ammonium IL was found to exhibit a mildly non-Arrhenius temperature dependence in the measured temperature range-indicative of molecular cooperativity. These differences in both local and long-range molecular dynamics are a direct reflection of the subtly different inter-ionic interactions and mesoscale structures found in these homologous ILs.« less

Recommendations for the Development of a Dust Suppressant Test Operations Procedure (TOP) Performed at the U.S. Army Yuma Proving Ground

DTIC Science & Technology

2010-02-08

variety of bedrock types including: igneous ( basalt , granite, and rhyolite), metamorphic (schist and gneiss), and sedimentary rocks of Quaternary...TerraLOC® Standard formulation was applied. Chemical dust suppressant formulations vary widely, to include salts, oils, fiber mixtures and synthetic

CAPILLARY ELECTROPHORESIS-ELECTROSPRAY MASS SPECTRA OF THE HERBICIDES PARAQUAT AND DIQUAT

EPA Science Inventory

The positive ion electrospray mass spectra of the quaternary ammonium salt herbicides paraquat and diquat are examined by on-line separation with capillary electrophoresis (CE) and by direct infusion of the analytes. The analytes are separated by CE in 7-10 min at pH 3.9 in 50% m...

Quaternary ammonium salts substituted by 5-phenyl-1,3,4-oxadiazole-2-thiol as novel antibacterial agents with low cytotoxicity.

PubMed

Wang, Chun-Hua; Xie, Xian-Rui; Liu, Wen-Shuai; Hou, Gui-Ge; Sun, Ju-Feng; Zhao, Feng; Cong, Wei; Li, Hong-Juan; Xin, Wen-Yu

2017-11-01

Twenty-one novel 5-phenyl-1,3,4-oxadiazole-2-thiol (POT) substituted N-hydroxyethyl quaternary ammonium salts (6a-g, 7a-g, 8a-g) were prepared and characterized by FTIR, NMR, and elemental analysis. Compounds 6a, 6c, and 8a were confirmed by X-ray single-crystal diffraction. They display the unsurpassed antibacterial activity against Staphylococcus aureus, α-H-tococcus, Escherichia coli, P. aeruginosa, Proteus vulgaris, Canidia Albicans, especially 6g, 7g, 8g with dodecyl group. Compounds 8a-d with N,N-dihydroxyethyl and POT groups display unsurpassed antibacterial activity and non-toxicity. The structure-activity relationships indicate that POT and flexible dihydroxyethyl group in QAS are necessary for antibacterial activity and cytotoxicity. SEM and TEM images of E. coli morphologies of 8d show the antibacterial agents can adhere to membrane surfaces to inhibit bacterial growth by disrupting peptidoglycan formation and releasing bacterial cytoplasm from cell membranes. © 2017 John Wiley & Sons A/S.

The smallest quaternary ammonium salts with ether groups for high-performance electrochemical double layer capacitors† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c5sc02755a Click here for additional data file.

PubMed Central

Han, Taihee; Park, Min-Sik; Kim, Jeonghun; Kim, Jung Ho

2016-01-01

Electrochemical double layer capacitors (EDLCs) are energy storage devices that have been used for a wide range of electronic applications. In particular, the electrolyte is one of the important components, directly related to the capacitance and stability. Herein, we first report a series of the smallest quaternary ammonium salts (QASs), with ether groups on tails and tetrafluoroborate (BF4) as an anion, for use in EDLCs. To find the optimal structure, various QASs with different sized head groups and ether-containing tail groups were systematically compared. Comparing two nearly identical structures with and without ether groups, QASs with oxygen atoms showed improved capacitance, proving that ions with oxygen atoms move more easily than their counterparts at lower electric fields. Moreover, the ether containing QASs showed low activation energy values of conductivities, leading to smaller IR drops during the charge and discharge processes, resulting in an overall higher capacitance. PMID:28959391

Physicochemical properties and solubility of alkyl-(2-hydroxyethyl)-dimethylammonium bromide.

PubMed

Domańska, Urszula; Bogel-Łukasik, Rafał

2005-06-23

Quaternary ammonium salts, which are precursors of ionic liquids, have been prepared from N,N-dimethylethanolamine as a substrate. The paper includes specific basic characterization of synthesized compounds via the following procedures: nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR) spectra, water content, mass spectroscopy (MS) spectra, temperatures of decompositions, basic thermodynamic properties of pure ionic liquids (the melting point, enthalpy of fusion, enthalpy of solid-solid phase transition, glass transition), and the difference in the solute heat capacity between the liquid and solid at the melting temperature determined by differential scanning calorimetry (DSC). The (solid + liquid) phase equilibria of binary mixtures containing (quaternary ammonium salt + water, or + 1-octanol) has been measured by a dynamic method over wide range of temperatures, from 230 K to 560 K. These data were correlated by means of the UNIQUAC ASM and modified nonrandom two-liquid NRTL1 equations utilizing parameters derived from the (solid + liquid) equilibrium. The partition coefficient of ionic liquid in the 1-octanol/water binary system has been calculated from the solubility results. Experimental partition coefficients (log P) were negative at three temperatures.

Ion pair-based liquid-phase microextraction combined with cuvetteless UV-vis micro-spectrophotometry as a miniaturized assay for monitoring ammonia in waters.

PubMed

Senra-Ferreiro, Sonia; Pena-Pereira, Francisco; Costas-Mora, Isabel; Romero, Vanesa; Lavilla, Isela; Bendicho, Carlos

2011-09-15

A miniaturized method based on liquid-phase microextraction (LPME) in combination with microvolume UV-vis spectrophotometry for monitoring ammonia in waters is proposed. The methodology is based on the extraction of the ion pair formed between the blue indophenol obtained according to the Berthelot reaction and a quaternary ammonium salt into a microvolume of organic solvent. Experimental parameters affecting the LPME performance such as type and concentration of the quaternary ammonium ion salt required to form the ion pair, type and volume of extractant solvent, effect of disperser solvent, ionic strength and extraction time, were optimized. A detection limit of 5.0 μg L(-1) ammonia and an enrichment factor of 30 can be attained after a microextraction time of 4 min. The repeatability, expressed as relative standard deviation, was 7.6% (n=7). The proposed method can be successfully applied to the determination of trace amounts of ammonia in several environmental water samples. Copyright © 2011 Elsevier B.V. All rights reserved.

High-sensitivity detection of polysaccharide using phosphodiesters quaternary ammonium salt as probe by decreased resonance light scattering.

PubMed

Chen, Zhanguang; Liu, Guoliang; Chen, Maohuai; Wu, Mingyao

2009-07-15

Phosphodiesters quaternary ammonium salt (PQAS) displayed quite intense light scattering in aqueous solution under the optimum condition. In addition, the resonance light scattering (RLS) signal of PQAS was remarkably decreased after adding trace amount polysaccharide with the maximum peak located at 391 nm. It was found that the decreased RLS intensity of the PQAS-PPGL system (DeltaI(RLS)) was in proportion to PPGL concentration in the range of 0.1-30 ng mL(-1), with a lower detection limit of 0.05 ng mL(-1). Based on this rare decreased RLS phenomenon, the novel method of the determination of purified polysaccharide of Gracilaria Lemaneiformis (PPGL) at nanogram level was proposed in this contribution. The proposed approach was used to determine purified polysaccharide extracted from Gracilaria Lemaneiformis with satisfactory results. Compared with the reported polysaccharide assays, this proposed method has good selectivity, high sensitivity and is especially simple and convenient. Moreover, the mechanism of the reaction between PQAS and polysaccharide was investigated by RLS, fluorescence, and fluorescence lifetime spectra.

Halogenated solvent interactions with N,N-dimethyltryptamine: formation of quaternary ammonium salts and their artificially induced rearrangements during analysis.

PubMed

Brandt, Simon D; Martins, Cláudia P B; Freeman, Sally; Dempster, Nicola; Riby, Philip G; Gartz, Jochen; Alder, John F

2008-07-04

The psychoactive properties of N,N-dimethyltryptamine (DMT) 1a are known to induce altered states of consciousness in humans. This particular attribute attracts great interest from a variety of scientific and also clandestine communities. Our recent research has confirmed that DMT reacts with dichloromethane (DCM), either as a result of work-up or storage to give a quaternary N-chloromethyl ammonium salt 2a. Furthermore, this was observed to undergo rearrangement during analysis using gas chromatography-mass spectrometry (GC-MS) with products including 3-(2-chloroethyl)indole 3 and 2-methyltetrahydro-beta-carboline 4 (2-Me-THBC). This study further investigates this so far unexplored area of solvent interactions by the exposure of DMT to other halogenated solvents including dibromomethane and 1,2-dichloroethane (DCE). The N-bromomethyl- and N-chloroethyl quaternary ammonium derivatives were subsequently characterised by ion trap GC-MS in electron and chemical ionisation tandem MS mode and by NMR spectroscopy. The DCE-derived derivative formed at least six rearrangement products in the total ion chromatogram. Identification of mass spectrometry generated by-products was verified by conventional or microwave-accelerated synthesis. The use of deuterated DCM and deuterated DMT 1b provided insights into the mechanism of the rearrangements. The presence of potentially characteristic marker molecules may allow the identification of solvents used during the manufacture of controlled substances, which is often neglected since these are considered inert.

Cyclohex-1-ene carboxylic acids: synthesis and biological evaluation of novel inhibitors of human 5 alpha reductase.

PubMed

Baston, Eckhard; Salem, Ola I A; Hartmann, Rolf W

2003-03-01

In search of novel nonsteroidal mimics of steroidal inhibitors of 5 alpha reductase, 4-(2-phenylethyl)cyclohex-1-ene carboxylic acids 1-5 were synthesized with different substituents in para position of the phenyl ring (1: N, N-diisopropylcarbamoyl, 2: phenyl, 3: phenoxy, 4: benzoyl, and 5: benzyl). The principal synthetic approach for the desired compounds consisted of a Wittig olefination between 1, 4-dioxaspiro [4.5]-decane-8-carbaldehyde (4g and the appropriate phosphonium salts. The compounds were tested for inhibition of human 5 alpha reductase isozymes 1 and 2 using DU 145 cells and preparations from prostatic tissue, respectively. They turned out to be good inhibitors of the prostatic isozyme 2 with compound 1 being the most potent one (IC(50) = 760 nM). Isozyme 1 was only slightly inhibited. It is concluded that the novel structures are appropriate for being further optimized, aiming at the development of a novel drug for the treatment of benign prostatic hyperplasia.

Structural insights into cholinesterases inhibition by harmane β-carbolinium derivatives: a kinetics-molecular modeling approach.

PubMed

Torres, Juliana M; Lira, Aline F; Silva, Daniel R; Guzzo, Lucas M; Sant'Anna, Carlos M R; Kümmerle, Arthur E; Rumjanek, Victor M

2012-09-01

The natural indole alkaloids, the β-carbolines, are often associated with cholinesterase inhibition, especially their quaternary salts, which frequently have higher activity than the free bases. Due to lack of information explaining this fact in the literature, the cholinesterase inhibition by the natural product harmane and its two β-carbolinium synthetic derivative salts (N-methyl and N-ethyl) was explored, together with a combination of kinetics and a molecular modeling approach. The results, mainly for the β-carbolinium salts, demonstrated a noncompetitive inhibition profile, ruling out previous findings which associated cholinesterase inhibition by β-carbolinium salts to a possible mimicking of the choline moiety of the natural substrate, acetylcholine. Molecular modeling studies corroborate this kind of inhibition through analyses of inhibitor/enzyme and inhibitor/substrate/enzyme complexes of both enzymes. Copyright © 2012 Elsevier Ltd. All rights reserved.

Palaeogeographic implications of the Messinian surface in the Valencia trough, northwestern Mediterranean Sea

NASA Astrophysics Data System (ADS)

Escutia, C.; Maldonado, A.

1992-03-01

Sparker (3000 J and 8000 J) and multichannel seismic reflection profiles across the Valencia trough show a Messinian unconformity incised by numerous valleys. The main feature of this surface is a large valley that generally underlies the present Valencia valley and is deeply entrenched into the Miocene deposits. The size of this palaeo-valley ranges from 0.5 km wide and 15-100 m deep at its western end, to 1.6-2.8 km wide and 200-250 m deep downstream. An important tributary system is observed, with a main canyon (6-8 km wide and 150-200 m deep) draining the Ebro margin, as well as many other smaller valleys draining the Catalan and Balearic margins. Downstream, other tributaries underlie the present canyons of the Catalan margin. The location of the tributary system is controlled by the Early Miocene rift structures. The relief of the Messinian surface is affected by post-Miocene deformation that results from salt diapirism, extensional faulting and related volcanism. Late Neogene to Quaternary volcanic edifices cut the Messinian surface and coincide with large residual magnetic anomalies. Lower Pliocene to Quaternary salt diapirism in the abyssal plain north of Menorca has created a series of structural highs. Between these highs are deep interdiapiric troughs or basins that have become sediment depocentres during the Plio-Quaternary. The complex network of erosional valleys from the Valencia trough continental margin demonstrates that the valley system in the basin was not related to the refilling of the Mediterranean, but to the Iberian and Balearic margin palaeodrainage that developed during the Messinian desiccation. The presence of at least three erosional unconformities suggests that there were alternating periods of flooding and retreat of Atlantic water during Messinian time. The Messinian subaerial margin with erosional valleys contrasts sharply with the Pliocene-Quaternary marine margin with progradational turbidite systems.

The dangerous new synthetic drug α-PVP as the hydrated chloride salt α-pyrrolidinopentiophenone hydrochloride 0.786-hydrate.

PubMed

Wood, Matthew R; Bernal, Ivan; Lalancette, Roger A

2016-01-01

α-Pyrrolidinovalerophenone (α-PVP), a dangerous designer drug, is now being marketed around the world as a harmless `bath salt', when in reality it is a powerful β-ketone phenethylamine stimulant. A sample of the free base from a recent law-enforcement seizure was crystallized as the HCl salt [systematic name: 1-(1-oxo-1-phenylpentan-2-yl)pyrrolidin-1-ium chloride 0.786-hydrate], C15H22NO(+)·Cl(-)·0.786H2O. In the crystal structure, the propyl chain is nearly perpendicular to both the phenyl ring and the carbonyl group. The hydrogen-bonding scheme involves the quaternary N atom, the Cl(-) anion and the partially occupied (0.786) water molecule, forming centrosymmetric dimers.

Acyclic N-Halamine Polymeric Biocidal Films

DTIC Science & Technology

2010-07-01

surfaces were rechargeable upon chlorine loss. antimicrobial, bacteria, biocidal coatings, biofilms , N-halamine U U U UU 14 Joe Wander 850 283-6240...halamine, biofilms , antimicrobial. INTRODUCTION A variety of antimicrobial organic materials, including phosp ho- nium salts [1-4], quaternary ammonium...Cotton Cellulose , J. Appl. Polym. Sci., 81: 617-624. 21. Sun, Y. and Sun, G. (2002). Durable and Regenerable Antimicrobial Textile Materials Prepared

Synthesis of Quaternary Ammonium Salts Based on Diketopyrrolopyrroles Skeletons and Their Applications in Copper Electroplating.

PubMed

Chen, Biao; Xu, Jie; Wang, Limin; Song, Longfeng; Wu, Shengying

2017-03-01

A series of DPP derivatives bearing quaternary ammonium salt centers with different lengths of carbon chains have been designed and synthesized. Their inhibition actions on copper electroplating were first investigated. A total of four diketopyrrolopyrrole (DPP) derivatives showed different inhibition capabilities on copper electroplating. To investigate interactions between metal surface and additives, we used quantum chemical calculations. Static and dynamic surface tension of four DPP derivatives had been measured, and the results showed DPP-10C (1c) with a faster-decreasing rate of dynamic surface tension among the four derivatives, which indicated higher adsorption rate of additive on the cathode surface and gives rise to stronger inhibiting effect of copper electrodeposition. Then, DPP-10C (1c) as the representative additive, was selected for the systematic study of the leveling influence during microvia filling through comprehensive electroplating tests. In addition, field-emission scanning electron microscope images and X-ray diffraction results showed the surface morphology, which indicated that addition of DPP derivative (1c) could lead a fine copper deposit and cause the preferential orientations of copper deposits to change from [220] to [111], which happened in particular at higher concentrations.

Effect of Quaternary Ammonium Salt on Shear Bond Strength of Orthodontic Brackets to Enamel

PubMed Central

Ghadirian, Hannaneh; Geramy, Allahyar; Najafi, Farhood; Heidari, Soolmaz

2017-01-01

Objectives: This study sought to assess the effect of quaternary ammonium salt (QAS) on shear bond strength of orthodontic brackets to enamel. Materials and Methods: In this in vitro experimental study, 0, 10, 20 and 30% concentrations of QAS were added to Transbond XT primer. Brackets were bonded to 60 premolar teeth using the afore-mentioned adhesive mixtures, and the shear bond strength of the four groups (n=15) was measured using a universal testing machine. After debonding, the adhesive remnant index (ARI) score was determined under a stereomicroscope. Data were analyzed using one-way ANOVA. Results: The mean and standard deviation of shear bond strength of the control and 10%, 20% and 30% groups were 23.54±6.31, 21.81±2.82, 20.83±8.35 and 22.91±5.66 MPa, respectively. No significant difference was noted in shear bond strength of the groups (P=0.83). Study groups were not different in terms of ARI scores (P=0.80). Conclusions: The results showed that addition of QAS to Transbond XT primer had no adverse effect on shear bond strength of orthodontic brackets. PMID:29167688

Removal of Remazol turquoise Blue G-133 from aqueous solution using modified waste newspaper fiber.

PubMed

Zhang, Xiaoyu; Tan, Jia; Wei, Xinhao; Wang, Lijuan

2013-02-15

Waste newspaper fiber (WNF) was separated and modified via grafting quaternary ammonium salt to obtain an adsorbent, which removes Remazol turquoise Blue G-133 (RTB G-133) from aqueous solutions. SEM and IR were used to analyze the morphology and chemical groups of the modified waste newspaper fiber (MWNF). Batch adsorption studies were conducted with varying adsorbent dosages, solution pH, and contact time. Adsorption isotherms and models were fitted. The SEM photographs show the surface of MWNF is smoother in comparison with that of WNF. The IR analysis indicates that the quaternary ammonium salt was successfully grafted onto the cellulose skeleton in WNF and the chemical interaction played an important role in adsorption. Results show that the equilibrium adsorption capacity can be reached within 360 min, and that the maximum adsorption capacity was 260 mg g(-1). The adsorption of RTB G-133 on MWNF was a spontaneous endothermic process and well fitted pseudo-second-order kinetic model and Langmuir adsorption isotherm model. The results show that MWNF is promising for dye wastewater treatment. Crown Copyright © 2012. Published by Elsevier Ltd. All rights reserved.

Reaction of N,N-Dimethyltryptamine with Dichloromethane Under Common Experimental Conditions.

PubMed

Dunlap, Lee E; Olson, David E

2018-05-31

A large number of clinically used drugs and experimental pharmaceuticals possess the N , N -dimethyltryptamine (DMT) structural core. Previous reports have described the reaction of this motif with dichloromethane (DCM), a common laboratory solvent used during extraction and purification, leading to the formation of an undesired quaternary ammonium salt byproduct. However, the kinetics of this reaction under various conditions have not been thoroughly described. Here, we report a series of experiments designed to simulate the exposure of DMT to DCM that would take place during extraction from plant material, biphasic aqueous work-up, or column chromatography purification. We find that the quaternary ammonium salt byproduct forms at an exceedingly slow rate, only accumulates to a significant extent upon prolonged exposure of DMT to DCM, and is readily extracted into water. Our results suggest that DMT can be exposed to DCM under conditions where contact times are limited (<30 min) with minimal risk of degradation and that this byproduct is not observed following aqueous extraction. However, alternative solvents should be considered when the experimental conditions require longer contact times. Our work has important implications for preparing a wide-range of pharmaceuticals bearing the DMT structural motif in high yields and purities.

Study on the effects of electrolytes and solvents in the determination of quaternary ammonium ions by nonaqueous capillary electrophoresis with contactless conductivity detection.

PubMed

Buglione, Lucia; See, Hong Heng; Hauser, Peter C

2013-01-01

A study on the separation of lipophilic quaternary ammonium cations in NACE coupled with contactless conductivity detection (NACE-C(4)D) is presented. The suitability of different salts dissolved in various organic solvents as running electrolytes in NACE-C(4)D was investigated. A solvent mixture of methanol/acetonitrile at a ratio of 90%:10% v/v showed the best results. Deoxycholic acid sodium salt as BGE was found to provide exceptional high stability with low baseline noise that leads to highest S/N ratios for the target analytes among all BGEs tested. Under the optimum conditions, capillaries with different internal diameters were examined and an id of 50 μm was found to give best detection sensitivity. The proposed method was validated and showed good linearity in the range from 2.5 to 200 μM, low limits of detection (0.1-0.7 μM) and acceptable reproducibility of peak area (intraday RSD 0.1-0.7%, n = 3; interday RSD 5.9-9.4%, n = 3). © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Design and Fabrication of Smart Diapers with Antibacterial Yarn

PubMed Central

Lin, Jia-Horng; Shiu, Bing-Chiuan; Lou, Ching-Wen

2017-01-01

In this study, intelligent eco-diapers are made by combining antibacterial yarns coated with quaternary ammonium salts with conductive yarns to improve caretaking for urinary incontinence. The combination of conductive yarns and sensors can detect the moisture content in eco-diapers, and an alarm is sent when moisture is significant. A wireless module is used to send detected signals to a smartphone or tablet PC via the Internet. This concept is used for a scenario in which nurses do not randomly check on patients in a long-term care institution. When used offline, eco-diapers can send caregivers an alarm for the need to change diapers via cell phones. The diameters of the copper and silver-plated copper fibers are 0.08 and 0.10 mm, respectively. Cotton yarns are twisted with copper and silver-plated copper fibers to form the conductive yarns, which are 0.12 mm in diameter. Moreover, 30-count cotton and 150 D nylon yarns are coated with quaternary ammonium salt via dyeing and finishing processes to form antibacterial yarns. In the current study, intelligent eco-diapers are tested for their electrical and antibacterial properties as specified by AATC and JISL test standards. PMID:29065646

Controlled release and long-term antibacterial activity of reduced graphene oxide/quaternary ammonium salt nanocomposites prepared by non-covalent modification.

PubMed

Ye, Xiaoli; Feng, Jin; Zhang, Jingxian; Yang, Xiujiang; Liao, Xiaoyan; Shi, Qingshan; Tan, Shaozao

2017-01-01

In order to control the long-term antibacterial property of quaternary ammonium salts, dodecyl dimethyl benzyl ammonium chloride (rGO-1227) and rGO-bromohexadecyl pyridine (rGO-CPB) were self-assembled on surfaces of reduced graphene oxide (rGO) via π-π interactions. The obtained rGO-1227 and rGO-CPB nanocompounds were characterized by X-ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), field emission scanning electron microscopy (FESEM), and transmission electron microscopy (TEM).The antibacterial activities were evaluated on Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus. Both rGO-CPB and rGO-1227 reduced the cytotoxicity of the pure antimicrobial agents and presented strong antimicrobial properties. Especially, CPB could be loaded efficiently on the surface of rGO via π-π conjugate effect, which resulted in a nanocomposite presenting a long-term antibacterial capability due to the more important quantity of free π electrons compared to that of 1227. When comparing the advantages of both prepared nanocomposites, rGO-CPB displayed a better specific-targeting capability and a longer-term antibacterial property. Copyright © 2016 Elsevier B.V. All rights reserved.

Biocidal and inhibitory activity screening of de novo synthesized surfactants against two eukaryotic and two prokaryotic microbial species.

PubMed

Tiecco, Matteo; Cardinali, Gianluigi; Roscini, Luca; Germani, Raimondo; Corte, Laura

2013-11-01

Thirty-six quaternary ammonium salts, of which 28 structurally different non-commercially available surfactants, were tested to screen their biocidal and inhibitory antimicrobial activity. Their activity was compared to commercially available amphiphiles as well as to non-amphiphilic quaternary ammonium salts. As target of these compounds four microbial species were employed of which two (Saccharomyces cerevisiae and Candida albicans) were important yeast in the food and clinical environment and the other two (Escherichia coli and Listeria innocua) represented the Gram negative and positive bacteria, respectively. The surfactants showed the ability to kill the microbial cells in water solution and to variably hamper their growth onto agar medium. The non-amphiphilic compounds (which represent analogues of some surfactants used in this study, since they have the same head group but no hydrophobic portion) had little effect in solution and no effect against the microbial growth on plate. Amphoteric and non-amphoteric zwitterionic surfactants showed reduced biocidal activity. The most active antimicrobial agent was N-tetradecyltropinium bromide (23S) surfactant. The presence of cells did not significantly affect the ability to form micelles, as demonstrated by comparative conductometric measurements. Copyright © 2013 Elsevier B.V. All rights reserved.

Antimicrobial activity of betaine esters, quaternary ammonium amphiphiles which spontaneously hydrolyze into nontoxic components.

PubMed Central

Lindstedt, M; Allenmark, S; Thompson, R A; Edebo, L

1990-01-01

A series of quaternary ammonium compounds that are esters of betaine and fatty alcohols with hydrocarbon chain lengths of 10 to 18 carbon atoms were tested with respect to antimicrobial activities and rates of hydrolysis. When the tetradecyl derivative was tested against some selected microorganisms, the killing effect was comparable to that of the stable quaternary ammonium compound cetyltrimethylammonium bromide. At higher pH values, both the antimicrobial effect and the rate of hydrolysis of the esters increased. However, whereas at pH 6 greater than 99.99% killing of Salmonella typhimurium was achieved with 5 micrograms/ml in 3 min, the rate of hydrolysis was less than 20% in 18 h. At pH 7, a similar killing effect was achieved in 2 min and 50% hydrolysis occurred in ca. 5 h. Thus, it is possible to exploit the rapid microbicidal effect of the compounds before they hydrolyze. The rate of hydrolysis was reduced by the presence of salt. The bactericidal effect of the betaine esters increased with the length of the hydrocarbon chain of the fatty alcohol moiety up to 18 carbon atoms. Since the hydrolysis products are normal human metabolites, the hydrolysis property may extend the use of these quaternary ammonium compounds as disinfectants and antiseptics for food and body surfaces. PMID:2291660

Phosphonium-Organophosphate Ionic Liquids as Lubricant Additives: Effects of Cation Structure on Physicochemical and Tribological Characteristics

DOE PAGES

Barnhill, William C.; Qu, Jun; Luo, Huimin; ...

2014-11-17

In our previous work we suggest great potential for a phosphonium-organophosphate ionic liquid (IL) as an antiwear lubricant additive. In this study, a set of five ILs were carefully designed and synthesized, with identical organophosphate anions but dissimilar phosphonium cations, to allow systematic investigation of the effects of cation alkyl chain length and symmetry on physicochemical and tribological properties. Symmetric cations with shorter alkyl chains seem to increase the density and thermal stability due to closer packing. On the other hand, either higher cation symmetry or longer alkyl moieties induce a higher viscosity, though the viscosity index is dependent moremore » on molecular mass than on symmetry. While a larger cation size generally increases an IL’s solubility in nonpolar hydrocarbon oils, six-carbon seems to be the critical minimum alkyl chain length for high oil miscibility. Both the two ILs, that are mutually oil miscible, have demonstrated promising lubricating performance at 1.04% treat rate, though the symmetric-cation IL moderately outperformed the asymmetric-cation IL. Moreover, characterizations on the tribofilm formed by the best-performing symmetric-cation IL revealed the film thickness, nanostructure, and chemical composition. Our results provide fundamental insights for future molecular design in developing oil-soluble ILs as lubricant additives.« less

Geohydrology of the northern Louisiana salt-dome basin pertinent to the storage of radioactive wastes; a progress report

USGS Publications Warehouse

Hosman, R.L.

1978-01-01

Salt domes in northern Louisiana are being considered as possible storage sites for nuclear wastes. The domes are in an area that received regional sedimentation through early Tertiary (Eocene) time with lesser amounts of Quaternary deposits. The Cretaceous-Tertiary accumulation is a few thousand feet thick; the major sands are regional aquifers that extend far beyond the boundaries of the salt-dome basin. Because of multiple aquifers, structural deformation, and variations in the hydraulic characteristics of cap rock, the ground-water hydrology around a salt dome may be highly complex. The Sparta Sand is the most productive and heavily used regional aquifer. It is either penetrated by or overlies most of the domes. A fluid entering the Sparta flow system would move toward one of the pumping centers, all at or near municipalities that pump from the Sparta. Movement could be toward surface drainage where local geologic and hydrologic conditions permit leakage to the surface or to a surficial aquifer. (Woodard-USGS)

CAD-DRASTIC: chloride application density combined with DRASTIC for assessing groundwater vulnerability to road salt application

NASA Astrophysics Data System (ADS)

Salek, Mansour; Levison, Jana; Parker, Beth; Gharabaghi, Bahram

2018-06-01

Road salt is pervasively used throughout Canada and in other cold regions during winter. For cities relying exclusively on groundwater, it is important to plan and minimize the application of salt accordingly to mitigate the adverse effects of high chloride concentrations in water supply aquifers. The use of geospatial data (road network, land use, Quaternary and bedrock geology, average annual recharge, water-table depth, soil distribution, topography) in the DRASTIC methodology provides an efficient way of distinguishing salt-vulnerable areas associated with groundwater supply wells, to aid in the implementation of appropriate management practices for road salt application in urban areas. This research presents a GIS-based methodology to accomplish a vulnerability analysis for 12 municipal water supply wells within the City of Guelph, Ontario, Canada. The chloride application density (CAD) value at each supply well is calculated and related to the measured groundwater chloride concentrations and further combined with soil media and aquifer vadose- and saturated-zone properties used in DRASTIC. This combined approach, CAD-DRASTIC, is more accurate than existing groundwater vulnerability mapping methods and can be used by municipalities and other water managers to further improve groundwater protection related to road salt application.

Metabolic Capability of a Predominant Halanaerobium sp. in Hydraulically Fractured Gas Wells and Its Implication in Pipeline Corrosion

PubMed Central

Liang, Renxing; Davidova, Irene A.; Marks, Christopher R.; Stamps, Blake W.; Harriman, Brian H.; Stevenson, Bradley S.; Duncan, Kathleen E.; Suflita, Joseph M.

2016-01-01

Microbial activity associated with produced water from hydraulic fracturing operations can lead to gas souring and corrosion of carbon-steel equipment. We examined the microbial ecology of produced water and the prospective role of the prevalent microorganisms in corrosion in a gas production field in the Barnett Shale. The microbial community was mainly composed of halophilic, sulfidogenic bacteria within the order Halanaerobiales, which reflected the geochemical conditions of highly saline water containing sulfur species (S2O32-, SO42-, and HS-). A predominant, halophilic bacterium (strain DL-01) was subsequently isolated and identified as belonging to the genus Halanaerobium. The isolate could degrade guar gum, a polysaccharide polymer used in fracture fluids, to produce acetate and sulfide in a 10% NaCl medium at 37°C when thiosulfate was available. To mitigate potential deleterious effects of sulfide and acetate, a quaternary ammonium compound was found to be an efficient biocide in inhibiting the growth and metabolic activity of strain DL-01 relative to glutaraldehyde and tetrakis (hydroxymethyl) phosphonium sulfate. Collectively, our findings suggest that predominant halophiles associated with unconventional shale gas extraction could proliferate and produce sulfide and acetate from the metabolism of polysaccharides used in hydraulic fracturing fluids. These metabolic products might be returned to the surface and transported in pipelines to cause pitting corrosion in downstream infrastructure. PMID:27446028

Evaluation of materials proposed for use in space flight

NASA Technical Reports Server (NTRS)

Duncan, W. C.

1981-01-01

The primary irritancy and allergenicity of flame resistant treated cotton knit shirts proposed for use in space flight were evaluated. The knitted shirts were supplied by NASA as follows: knitted shirts with collars were made of two-ply mercerized single-knit cotton jersey. The fabric was treated with tetrakis (hydroxymethyl) phosphonium hydroxide and subsequently cured with gaseous ammonia (THPOH/NH3). The final treatment comprised adding on diammonium phosphate (DAP)/urea. The treated fabric was process scoured to remove extraneous materials, top softened and mechanically or chemically finished as required for specific needs. Diammonium phosphate is a more efficient flame inhabitant than the phosphonium; thus, the combination treatment served to impart higher resistance to ignition and sustained combustion as required by NASA test standard.

Seismic evidence of Messinian salt in opposite margins of West Mediterranean

NASA Astrophysics Data System (ADS)

Mocnik, Arianna; Camerlenghi, Angelo; Del Ben, Anna; Geletti, Riccardo; Wardell, Nigel; Zgur, Fabrizio

2015-04-01

The post drift Messinian Salinity Crisis (MSC) affected the whole Mediterranean basin, with deposition of evaporitic sequences in the deep basins, in the lower continental slopes, and in several shallower marginal basins; usually, in the continental margins, the MSC originated noticeable erosional truncations that locally cause important hiatuses in the pre-Messinian sequences, covered by the Plio-Quaternary sediments. In this work we focus on the MSC seismic signature of two new seismic datasets acquired in 2010 (West Sardinia offshore) and in 2012 (within the Eurofleet project SALTFLU in the South Balearic continental margin and the northern Algero abyssal plain). The "Messinian trilogy" recognized in the West-Mediterranean abyssal plain, is characterized by different seismic facies: the Lower evaporite Unit (LU), the salt Mobile Unit (MU) and the Upper evaporite mainly gypsiferous Unit (UU). Both seismic datasets show the presence of the Messinian trilogy also if the LU is not always clearly interpretable due to the strong seismic signal absorption by the halite layers; the salt thickness of the MU is similar in both the basins as also the thickness and stratigraphy of the UU. The Upper Unit (UU) is made up of a well reflecting package of about 10 reflectors, partially deformed by salt tectonic and characterized by a thin transparent layer that we interpreted as salt sequence inner the shallower part of the UU. Below the stratified UU, the MU exhibits a transparent layer in the deep basin and also on the foot of the slope, where a negative reflector, related to the high interval velocity of salt, marks its base. The halokinetic processes are not homogeneously distributed in the region, forming a great number of diapirs on the foot of the slope (due to the pression of the slided sediments) and giant domes toward the deep basin (due to the higher thickness of the Plio-quaternary sediments). This distribution seems to be related to the amount of salt and of the sedimentary cover. During the MSC the margins of the West Mediterranean Sea seem to be involved in some tectonic events probably connected to reactivation of normal faults and to the fast variation of the water load related to sea level fluctuations. The absence of calibrating boreholes in the deep Mediterranean basins and the hard penetration of seismic energy below the evaporitic layers, represent a limit for the knowledge of the geological evolution of the basins; the interpretation of the presented datasets could be a contribution to the comprehension of the evaporitic deposition and early-stage salt deformation during the MSC in the Mediterranean sea.

Phase Diagram of Quaternary System NaBr-KBr-CaBr2-H2O at 323 K

NASA Astrophysics Data System (ADS)

Cui, Rui-Zhi; Wang, Wei; Yang, Lei; Sang, Shi-Hua

2018-03-01

The phase equilibria in the system NaBr-KBr-CaBr2-H2O at 323 K were studied using the isothermal dissolution equilibrium method. Using the experimental solubilities of salts data, phase diagram was constructed. The phase diagram have two invariant points, five univariant curves, and four crystallization fields. The equilibrium solid phases in the system are NaBr, NaBr · 2H2O, KBr, and CaBr2 · 4H2O. The solubilities of salts in the system at 323 K were calculated by Pitzer's equation. There is shown that the calculated solubilities agree well with experimental data.

Stabilization of molten salt materials using metal chlorides for solar thermal storage.

PubMed

Dunlop, T O; Jarvis, D J; Voice, W E; Sullivan, J H

2018-05-29

The effect of a variety of metal-chlorides additions on the melting behavior and thermal stability of commercially available salts was investigated. Ternary salts comprised of KNO 3, NaNO 2, and NaNO 3 were produced with additions of a variety of chlorides (KCl, LiCl, CaCl 2 , ZnCl 2 , NaCl and MgCl 2 ). Thermogravimetric analysis and weight loss experiments showed that the quaternary salt containing a 5 wt% addition of LiCl and KCl led to an increase in short term thermal stability compared to the ternary control salts. These additions allowed the salts to remain stable up to a temperature of 630 °C. Long term weight loss experiments showed an upper stability increase of 50 °C. A 5 wt% LiCl addition resulted in a weight loss of only 25% after 30 hours in comparison to a 61% loss for control ternary salts. Calorimetry showed that LiCl additions allow partial melting at 80 °C, in comparison to the 142 °C of ternary salts. This drop in melting point, combined with increased stability, provided a molten working range increase of almost 100 °C in total, in comparison to the control ternary salts. XRD analysis showed the oxidation effect of decomposing salts and the additional phase created with LiCl additions to allow melting point changes to occur.

The promotion of geomorphosites on salt from Sovata - Praid and Turda using cultural and scientific tourism

NASA Astrophysics Data System (ADS)

Toma, B.; Irimus, I.; Petrea, D.

2012-04-01

The paper highlights the role of geomorphosites on salt, in experts and specialists training, in geography of tourism and planning, namely, the involvement of educational factor in defining managerial and marketing skills of future specialists in training. Geographical area of investigation belongs to the Transylvanian tectonic basin, overlapped to saliferous tectonic area from eastern Transylvania, represented by Praid - Sovata - Corund anticline and Sic -Cojocna - Turda anticline, analysis is focused on the Praid - Sovata and Turda diapirs. Saliferous area Praid - Sovata - Corund is situated on the contact area of the Transylvanian Basin with neo-eruptiv mountain chain of Eastern Carpathians, Calimani - Gurghiu - Harghita, and at the contact of Târnavelor Plateau with the orogen alignment of Gurghiu - Harghita Mountains. The salt body, in the horizontal plane, has a quasi-circular shape, slightly ellipsoidal, with diameters of 1.2 and 1.4 km, and is estimated to have a burial depth of 2.6 to 2.8 km. The salt massif from Praid, pierce the Mio-Pliocene blanket around and appears at the surface as diapir, flanked by sedimentary rocks that are partially covered by extrusive post-Pliocene volcanic formations and Quaternary deposits. Evaporitic deposits presents a varied lithology represented by gypsum, anhydrite, salt rock, potassium salt and celestine. The salt massif from Turda develops on the anticline Sic -Cojocna - Turda, oriented NE - SW, 2 km NE of Turda's downtown. It has an elongated shape, about 4 km, with widths ranging from 700 m to 200 m and also with a thickness ranging from 750 m to over 1000 m. In terms of stratigraphy, the salt massif is surrounded by deposits belonging to Badenian, Sarmatian and Quaternary. Due to salt dissolution by meteoric waters, carsto-saline lakes were formed, and due to ceiling collapse, because of an intensive exploitation, and infiltrations of rainwater and rivers, antropo-salted lakes were formed. The water and mud of these lakes are used for external treatment. The holes resulting from exploitation were arranged and turned into treatment rooms for those affected by respiratory diseases. Localities Praid and Sovata from rural settlements, have become balneary resorts, that use these salt resources by multiple forms of tourism: spas, climatic, cultural, recreational and scientific. In Turda has developed both health, climacteric and recreational tourism, as well as cultural and historical tourism, given the historical relics that are housed here. The design of applicative segment of geomorphological sites on salt recovery, through tourism activities is the objective of our work. Methodological argumentation is supported by the objective motivation, of geomorphosites on salt capitalization, by the content of syllabus and specialization of geography of tourism and territorial planning, from the Faculty of Geography, Babes-Bolyai University from Cluj-Napoca. The syllabus content argues the need for knowledge of geomorphosites genesis, their morphology, touristic valences, urbanistic valences, and the possibility of recovery, through forms and types of tourism, namely, urban, agricultural, industrial forms and types of exploitation. Key words: salt, geomorphosites, Praid, Turda, recovery

N,N-Dimethyltryptamine and dichloromethane: rearrangement of quaternary ammonium salt product during GC-EI and CI-MS-MS analysis.

PubMed

Brandt, Simon D; Martins, Cláudia P B; Freeman, Sally; Dempster, Nicola; Wainwright, Mark; Riby, Philip G; Alder, John F

2008-05-12

N,N-Dimethyltryptamine (DMT) 1 is a simple tryptamine derivative with powerful psychoactive properties. It is abundant in nature and easily accessible through a variety of synthetic routes. Most work-up procedures require the use of organic solvents and halogenated representatives are often employed. DMT was found to be reactive towards dichloromethane, either during work-up or long term storage therein, which led to the formation of the quaternary ammonium salt N-chloromethyl-DMT chloride 2. Analysis of this side-product by gas chromatography ion trap mass spectrometry (GC-MS), both in electron and chemical ionisation tandem MS modes, gave only degradation products. For example, 2 could not be detected but appeared to have rearranged to 3-(2-chloroethyl)indole 3 and 2-methyltetrahydro-beta-carboline 4, whereas HPLC analysis enabled the detection of 2. GC-MS is a standard tool for the fingerprinting of drug products. The identification of a particular synthetic route is based on the analysis of impurities, provided these side products can be established to be route-specific. The in situ detection of both 3 and 4 within a DMT sample may have led to erroneous conclusions with regards to the identification of the synthetic route.

Phosphonium carbosilane dendrimers - interaction with a simple biological membrane model.

PubMed

Wrobel, Dominika; Kubikova, Radka; Müllerová, Monika; Strašák, Tomas; RůŽička, Květoslav; Fulem, Michal; Maly, Jan

2018-05-30

The influence of three generations of five different phosphonium carbosilane dendrimers and one ammonium carbosilane dendrimer as a reference (PMe3, PBu3, P(Et2)2(CH2)3OH, PPh3, P(MeOPh)3 and NMe3, peripheral functional groups) on dimyristoylphosphatidylcholine (DMPC) or a lipid mixture dimyristoylphosphatidylcholine/dimyristoylphosphatidylglycerol (DMPC/DMPG) of liposomes was studied by fluorescence polarization measurements and differential scanning calorimetry. All types of dendrimers interacted with neutral as well as negatively charged liposomes, but the strength and observed influence were different. Concentration, type of peripheral functional group modification and dendrimer generation were the main factors influencing the interaction. Generally, weak interactions as well as destabilization of the lipid membranes at low concentrations, regardless of liposome type, were observed in the case of DmPMe3, DmNMe3, DmPBu3 and DmP(Et2)2(CH2)3OH. Dendrimers with PPh3 and P(MeOPh)3 peripheral functional groups interacted much more strongly and increased the rigidity of liposomes. Electrostatic interactions, the hydrophobicity of substituents and charge shielding on the peripheral phosphonium group are important factors in the interaction. We suggest that, among the other types of dendrimers, the dendrimer with the P(MeOPh)3 peripheral functional group is a highly promising candidate for the design of a drug delivery system due to its positive charge, efficient interaction with lipidic membranes and low cytotoxicity.

Understanding the Chemical Reactivity of Phosphonium-Based Ionic Liquids with Tellurium.

PubMed

Zhang, Tao; Schwedtmann, Kai; Weigand, Jan J; Doert, Thomas; Ruck, Michael

2018-05-15

The chemical reactivity of phosphonium based ionic liquids (ILs) towards tellurium at temperatures above 220 °C was systematically investigated by a series of dissolution experiments, tracking the solute tellurium species by nuclear magnetic resonance, and characterizing the reaction products by X-ray diffraction and scanning electron microscopy. The initial step is the thermal elimination of an alkyl group of the phosphonium cation of the ILs, most probably via an S N 2 mechanism. The addition of tellurium follows to form trialkylphosphane tellurides as evidenced by 31 P and 125 Te NMR spectroscopic experiments. The trialkylphosphane tellurides can serve as a tellurium reservoir for the formation of metal tellurides, like Bi 2 Te 3 and Ag 2 Te. It was observed that trihexyltetradecylphosphonium chloride ([P 6 6 6 14 ]Cl) shows a very weak reactivity that is reflected by a low solubility of tellurium, while trihexyltetradecylphosphonium dicyanamide/decanoate ([P 6 6 6 14 ][N(CN) 2 ]/[P 6 6 6 14 ][decanoate]) and tetrabutylphosphonium decanoate ([P 4 4 4 4 ][decanoate]) dissolve tellurium to a much higher extent. We attribute these observations to the different Lewis basicity of the anions of the ILs as main influencing factor. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fault Activity in the Terrebonne Trough, Southeastern Louisiana: A Continuation of Salt-Withdrawal Fault Activity from the Miocene into the late Quaternary and Implication for Subsidence Hot-Spots

NASA Astrophysics Data System (ADS)

Akintomide, A. O.; Dawers, N. H.

2017-12-01

The observed displacement along faults in southeastern Louisiana has raised questions about the kinematic history of faults during the Quaternary. The Terrebonne Trough, a Miocene salt withdrawal basin, is bounded by the Golden Meadow fault zone on its northern boundary; north dipping, so-called counter-regional faults, together with a subsurface salt ridge, define its southern boundary. To date, there are relatively few published studies on fault architecture and kinematics in the onshore area of southeastern Louisiana. The only publically accessible studies, based on 2d seismic reflection profiles, interpreted faults as mainly striking east-west. Our interpretation of a 3-D seismic reflection volume, located in the northwestern Terrebonne Trough, as well as industry well log correlations define a more complex and highly-segmented fault architecture. The northwest striking Lake Boudreaux fault bounds a marsh on the upthrown block from Lake Boudreaux on the downthrown block. To the east, east-west striking faults are located at the Montegut marsh break and north of Isle de Jean Charles. Portions of the Lake Boudreaux and Isle de Jean Charles faults serve as the northern boundary of the Madison Bay subsidence hot-spot. All three major faults extend to the top of the 3d seismic volume, which is inferred to image latest Pleistocene stratigraphy. Well log correlation using 11+ shallow markers across these faults and kinematic techniques such as stratigraphic expansion indices indicate that all three faults were active in the middle(?) and late Pleistocene. Based on expansion indices, both the Montegut and Isle de Jean Charles faults were active simultaneously at various times, but with different slip rates. There are also time intervals when the Lake Boudreaux fault was slipping at a faster rate compared to the east-west striking faults. Smaller faults near the margins of the 3d volume appear to relate to nearby salt stocks, Bully Camp and Lake Barre. Our work to date suggests both salt and fault activity continued at least into the latest Pleistocene.

Functionalizing aluminum substrata by quaternary ammonium for antifouling performances

NASA Astrophysics Data System (ADS)

He, Xiaoyan; Suo, Xinkun; Bai, Xiuqin; Yuan, Chengqing; Li, Hua

2018-05-01

Due to the great loss induced by biofouling, developing new strategies for combating biofouling has attracted extensive attention. Quaternary ammonium salts are potent cationic antimicrobials used in consumer products and their use for surface immobilization could create a contact-active antimicrobial layer. Here we report the facile preparation of a contact-active antifouling coating by tethering polyethyleneimine (PEI) onto flat/nanostructured aluminum surface by hydrogen bonding between PEI and AlOOH. Quaternized PEI (QPEI) is obtained through quaternization reactions. Biofouling testing suggests excellent antifouling performances of the samples by declining the adhesion of 95% Phaeodactylum tricornutum and 98% of Chlorella pyrenoidosa. The antifouling properties of PEI/QPEI are attributed predominately to their hydrophilic and antimicrobial nature. The technical route of PEI/QPEI surface grafting shows great potential for modifying marine infrastructures for enhanced antifouling performances.

Non-toxic fluorescent phosphonium probes to detect mitochondrial potential.

PubMed

Šarić, Ana; Crnolatac, Ivo; Bouillaud, Frédéric; Sobočanec, Sandra; Mikecin, Ana-Matea; Mačak Šafranko, Željka; Delgeorgiev, Todor; Piantanida, Ivo; Balog, Tihomir; Petit, Patrice X

2017-03-22

We evaluated our phosphonium-based fluorescent probes for selective staining of mitochondria. Currently used probes for monitoring mitochondrial membrane potential show varying degrees of interference with cell metabolism, photo-induced damage and probe binding. Here presented probes are characterised by highly efficient cellular uptake and specific accumulation in mitochondria. Fluorescent detection of the probes was accomplished using flow cytometry and confocal microscopy imaging of yeast and mammalian cells. Toxicity analysis (impedimetry-xCELLigence for the cellular proliferation and Seahorse technology for respiratory properties) confirms that these dyes exhibit no-toxicity on mitochondrial or cellular functioning even for long time incubation. The excellent chemical and photophysical stability of the dyes makes them promising leads toward improved fluorescent probes. Therefore, the probes described here offer to circumvent the problems associated with existing-probe's limitations.

Non-toxic fluorescent phosphonium probes to detect mitochondrial potential

NASA Astrophysics Data System (ADS)

Šarić, Ana; Crnolatac, Ivo; Bouillaud, Frédéric; Sobočanec, Sandra; Mikecin, Ana-Matea; Mačak Šafranko, Željka; Delgeorgiev, Todor; Piantanida, Ivo; Balog, Tihomir; Petit, Patrice X.

2017-03-01

We evaluated our phosphonium-based fluorescent probes for selective staining of mitochondria. Currently used probes for monitoring mitochondrial membrane potential show varying degrees of interference with cell metabolism, photo-induced damage and probe binding. Here presented probes are characterised by highly efficient cellular uptake and specific accumulation in mitochondria. Fluorescent detection of the probes was accomplished using flow cytometry and confocal microscopy imaging of yeast and mammalian cells. Toxicity analysis (impedimetry—xCELLigence for the cellular proliferation and Seahorse technology for respiratory properties) confirms that these dyes exhibit no-toxicity on mitochondrial or cellular functioning even for long time incubation. The excellent chemical and photophysical stability of the dyes makes them promising leads toward improved fluorescent probes. Therefore, the probes described here offer to circumvent the problems associated with existing-probe’s limitations.

Presidential Green Chemistry Challenge: 1997 Designing Greener Chemicals Award

EPA Pesticide Factsheets

Presidential Green Chemistry Challenge 1997 award winner, Albright & Wilson Americas, discovered that tetrakis(hydroxymethyl)phosphonium sulfate, THPS, is an effective, safer biocide for use in industrial water systems.

Composite Environmental Statement for Operations and Maintenance of Four Projects in the Mermentau Basin, Louisiana.

DTIC Science & Technology

1981-10-01

heavy metals, or petroleum hydrocarbons in the tissues of marine organisms was evaluated by laboratory methodologies for the winter (120C) and...for trans- port of petroleum , marine shells, supply boats for these industries, and commercial fishing boats. Flood control protection will continue to...emergent salt domes, are entirely Quaternary (Pleistocene and Holocene) in age. d. Economic geology. Sand and petroleum are the principal pro- ducts

Synthesis, antimicrobial evaluation and molecular modeling of 5-hydroxyisoquinolinium salt series; the effect of the hydroxyl moiety.

PubMed

Soukup, Ondrej; Dolezal, Rafael; Malinak, David; Marek, Jan; Salajkova, Sarka; Pasdiorova, Marketa; Honegr, Jan; Korabecny, Jan; Nachtigal, Petr; Nachon, Florian; Jun, Daniel; Kuca, Kamil

2016-02-15

In the present paper, we describe the synthesis of a new group of 5-hydroxyisoquinolinium salts with different lengths of alkyl side-chain (C10-C18), and their chromatographic analysis and biological assay for in vitro activity against bacterial and fungal strains. We compare the lipophilicity and efficacy of hydroxylated isoquinolinium salts with the previously published (non-hydroxylated) isoquinolinium salts from the point of view of antibacterial and antifungal versatility and cytotoxic safety. Compound 11 (C18) had to be excluded from the testing due to its low solubility. Compounds 9 and 10 (C14, C16) showed only moderate efficacy against G+ bacteria, notably with excellent potency against Staphyloccocus aureus, but no effect against G- bacteria. In contrast, non-hydroxylated isoquinolinium salts showed excellent antimicrobial efficacy within the whole series, particularly 14 (C14) against G+ strains and 15 (C16) against fungi. The electronic properties and desolvation energies of 5-hydroxyisoquinolinium and isoquinolinium salts were studied by quantum-chemistry calculations employing B3LYP/6-311++G(d,p) method and an implicit water-solvent simulation model (SCRF). Despite the positive mesomeric effect of the hydroxyl moiety reducing the electron density of the quaternary nitrogen, it is probably the higher lipophilicity and lower desolvation energy of isoquinolinium salts, which is responsible for enhanced antimicrobial versatility and efficacy. Copyright © 2016 Elsevier Ltd. All rights reserved.

Determination of the quaternary phase diagram of the water-ethylene glycol-sucrose-NaCl system and a comparison between two theoretical methods for synthetic phase diagrams

PubMed Central

Han, Xu; Liu, Yang; Critser, John K.

2010-01-01

Characterization of the thermodynamic properties of multi-solute aqueous solutions is of critical importance for biological and biochemical research. For example, the phase diagrams of aqueous systems, containing salts, saccharides, and plasma membrane permeating solutes, are indispensible in the field of cryobiology and pharmacology. However, only a few ternary phase diagrams are currently available for these systems. In this study, an auto-sampler differential scanning calorimeter (DSC) was used to determine the quaternary phase diagram of the water-ethylene glycol-sucrose-NaCl system. To improve the accuracy of melting point measurement, a “mass redemption” method was also applied for the DSC technique. Base on the analyses of these experimental data, a comparison was made between the two practical approaches to generate phase diagrams of multi-solute solutions from those of single-solute solutions: the summation of cubic polynomial melting point equations versus the use of osmotic virial equations with cross coefficients. The calculated values of the model standard deviations suggested that both methods are satisfactory for characterizing this quaternary system. PMID:20447385

Biodiversity of soil bacteria exposed to sub-lethal concentrations of phosphonium-based ionic liquids: Effects of toxicity and biodegradation.

PubMed

Sydow, Mateusz; Owsianiak, Mikołaj; Framski, Grzegorz; Woźniak-Karczewska, Marta; Piotrowska-Cyplik, Agnieszka; Ławniczak, Łukasz; Szulc, Alicja; Zgoła-Grześkowiak, Agnieszka; Heipieper, Hermann J; Chrzanowski, Łukasz

2018-01-01

Little is known about the effect of ionic liquids (ILs) on the structure of soil microbial communities and resulting biodiversity. Therefore, we studied the influence of six trihexyl(tetradecyl)phosphonium ILs (with either bromide or various organic anions) at sublethal concentrations on the structure of microbial community present in an urban park soil in 100-day microcosm experiments. The biodiversity decreased in all samples (Shannon's index decreased from 1.75 down to 0.74 and OTU's number decreased from 1399 down to 965) with the largest decrease observed in the microcosms spiked with ILs where biodegradation extent was higher than 80%. (i.e. [P 66614 ][Br] and [P 66614 ][2,4,4]). Despite this general decrease in biodiversity, which can be explained by ecotoxic effect of the ILs, the microbial community in the microcosms was enriched with Gram-negative hydrocarbon-degrading genera e.g. Sphingomonas. It is hypothesized that, in addition to toxicity, the observed decrease in biodiversity and change in the microbial community structure may be explained by the primary biodegradation of the ILs or their metabolites by the mentioned genera, which outcompeted other microorganisms unable to degrade ILs or their metabolites. Thus, the introduction of phosphonium-based ILs into soils at sub-lethal concentrations may result not only in a decrease in biodiversity due to toxic effects, but also in enrichment with ILs-degrading bacteria. Copyright © 2017 Elsevier Inc. All rights reserved.

64Cu-Labeled Phosphonium Cations as PET Radiotracers for Tumor Imaging

PubMed Central

Zhou, Yang; Liu, Shuang

2011-01-01

Alteration in mitochondrial transmembrane potential (ΔΨm) is an important characteristic of cancer. The observation that the enhanced negative mitochondrial potential is prevalent in tumor cell phenotype provides a conceptual basis for development of mitochondrion-targeting therapeutic drugs and molecular imaging probes. Since plasma and mitochondrial potentials are negative, many delocalized organic cations, such as rhodamine-123 and 3H-tetraphenylphosphonium, are electrophoretically driven through these membranes, and able to localize in the energized mitochondria of tumor cells. Cationic radiotracers, such as 99mTc-Sestamibi and 99mTc-Tetrofosmin, have been clinically used for diagnosis of cancer by single photon emission computed tomography (SPECT) and noninvasive monitoring of the multidrug resistance (MDR) transport function in tumors of different origin. However, their diagnostic and prognostic values are often limited due to their insufficient tumor localization (low radiotracer tumor uptake) and high radioactivity accumulation in the chest and abdominal regions (low tumor selectivity). In contrast, the 64Cu-labeled phosphonium cations represent a new class of PET (positron emission tomography) radiotracers with good tumor uptake and high tumor selectivity. This review article will focus on our recent experiences in evaluation of 64Cu-labeled phosphonium cations as potential PET radiotracers. The main objective is to illustrate the impact of radiometal chelate on physical, chemical and biological properties of 64Cu radiotracers. It will also discuss some important issues related to their tumor selectivity and possible tumor localization mechanism. PMID:21696200

Do group 1 metal salts form deep eutectic solvents?

PubMed

Abbott, A P; D'Agostino, C; Davis, S J; Gladden, L F; Mantle, M D

2016-09-14

Mixtures of metal salts such as ZnCl 2 , AlCl 3 and CrCl 3 ·6H 2 O form eutectic mixtures with complexing agents, such as urea. The aim of this research was to see if alkali metal salts also formed eutectics in the same way. It is shown that only a limited number of sodium salts form homogeneous liquids at ambient temperatures and then only with glycerol. None of these mixtures showed eutectic behaviour but the liquids showed the physical properties similar to the group of mixtures classified as deep eutectic solvents. This study focussed on four sodium salts: NaBr, NaOAc, NaOAc·3H 2 O and Na 2 B 4 O 7 ·10H 2 O. The ionic conductivity and viscosity of these salts with glycerol were studied, and it was found that unlike previous studies of quaternary ammonium salts with glycerol, where the salt decreased the viscosity, most of the sodium salts increased the viscosity. This suggests that sodium salts have a structure making effect on glycerol. This phenomenon is probably due to the high charge density of Na + , which coordinates to the glycerol. 1 H and 23 Na NMR diffusion and relaxation methods have been used to understand the molecular dynamics in the glycerol-salt mixtures, and probe the effect of water on some of these systems. The results reveal a complex dynamic behaviour of the different species within these liquids. Generally, the translational dynamics of the 1 H species, probed by means of PFG NMR diffusion coefficients, is in line with the viscosity of these liquids. However, 1 H and 23 Na T 1 relaxation measurements suggest that the Na-containing species also play a crucial role in the structure of the liquids.

Density-dependent groundwater flow and dissolution potential along a salt diapir in the Transylvanian Basin, Romania

NASA Astrophysics Data System (ADS)

Zechner, Eric; Danchiv, Alex; Dresmann, Horst; Mocuţa, Marius; Huggenberger, Peter; Scheidler, Stefan; Wiesmeier, Stefan; Popa, Iulian; Zlibut, Alexandru; Zamfirescu, Florian

2016-04-01

Salt diapirs and the surrounding sediments are often involved in a variety of human activities, such as salt mining, exploration and storage of hydrocarbons, and also storage of radioactive waste material. The presence of highly soluble evaporitic rocks, a complex tectonic setting related to salt diapirsm, and human activities can lead to significant environmental problems, e.g. land subsidence, sinkhole development, salt cavern collapse, and contamination of water resources with brines. In the Transylvanian town of Ocna Mures. rock salt of a near-surface diapir has been explored since the Roman ages in open excavations, and up to the 20th century in galleries and with solution mining. Most recently, in 2010 a sudden collapse in the adjacent Quaternary unconsolidated sediments led to the formation of a 70-90m wide salt lake with a max. depth of 23m. Over the last 3 years a Romanian-Swiss research project has led to the development of 3D geological and hydrogeological information systems in order to improve knowledge on possible hazards related to uncontrolled salt dissolution. One aspect which has been investigated is the possibility of density-driven flow along permeable subvertical zones next to the salt dome, and the potential for subsaturated groundwater to dissolve the upper sides of the diapir. Structural 3D models of the salt diapir, the adjacent basin sediments, and the mining galleries, led to the development of 2D numerical vertical density-dependent models of flow and transport along the diapir. Results show that (1) increased rock permeability due to diapirsm, regional tectonic thrusting and previous dissolution, and (2) more permeable sandstone layers within the adjacent basin sediments may lead to freshwater intrusion towards the top of the diapir, and, therefore, to increased potential for salt dissolution.

Role of Growth Faulting in the Quaternary Development of Mississippi-River Delta

NASA Astrophysics Data System (ADS)

Mohrig, D.; George, T. J.; Straub, K. M.

2008-12-01

We use an industry grade seismic volume and observations of present-day surface topography to resolve the influence of growth faulting on evolution of Mississippi delta in southeastern Louisiana from the Pleistocene to Recent. The volume of seismic data covers an area roughly 1400 square kilometers in size and it resolves many normal faults with displacements that can be tied to movement of Jurassic Louann Salt in the subsurface. We have defined the Quaternary activity associated with 6 of these normal faults by measuring the progressive offset of strata deposited on the delta surface over time. These measurements of fault displacement were restricted to the sedimentary section positioned 150 to 1500 m beneath the delta surface. Total vertical offsets measured within this Quaternary section range from 60 to 150 m. These fault displacements represent abrupt spatial variations in subsidence rate that are between 4 and 8 percent of the regional, long-term deposition rate. Our best estimates for the Quaternary rates of fault displacement vary between 0.1 and 1 mm/yr. Five faults can be connected to deformation of the modern delta surface. Wetland on the footwall is replaced by open water on the hanging wall of these structures. In spite of this evidence for modern surface deformation, the orientations of buried, seismically resolved channel bodies do not appear to be affected by the positions of active growth faults. We will evaluate the competition between subsidence and sedimentation patterns that leads to this style of channelized stratigraphy.

Aluminum electroplating on steel from a fused bromide electrolyte

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prabhat K. Tripathy; Laura A. Wurth; Eric J. Dufek

A quaternary bromide bath (LiBr–KBr–CsBr–AlBr3) was used to electro-coat aluminum on steel substrates. The electrolytewas prepared by the addition of AlBr3 into the eutectic LiBr–KBr–CsBr melt. A smooth, thick, adherent and shiny aluminum coating could be obtained with 80 wt.% AlBr3 in the ternary melt. The SEM photographs of the coated surfaces suggest the formation of thick and dense coatings with good aluminum coverage. Both salt immersion and open circuit potential measurement suggested that the coatings did display a good corrosionresistance behavior. Annealing of the coated surfaces, prior to corrosion tests, suggested the robustness of the metallic aluminum coating inmore » preventing the corrosion of the steel surfaces. Studies also indicated that the quaternary bromide plating bath can potentially provide a better aluminumcoating on both ferrous and non-ferrous metals, including complex surfaces/geometries.« less

Agulhas leakage as a key process in the modes of Quaternary climate changes.

PubMed

Caley, Thibaut; Giraudeau, Jacques; Malaizé, Bruno; Rossignol, Linda; Pierre, Catherine

2012-05-01

Heat and salt transfer from the Indian Ocean to the Atlantic Ocean (Agulhas leakage) has an important effect on the global thermohaline circulation and climate. The lack of long transfer record prevents elucidation of its role on climate changes throughout the Quaternary. Here, we present a 1,350-ka accumulation rate record of the planktic foraminiferal species Globorotalia menardii. We demonstrate that, according to previous assumptions, the presence and reseeding of this fauna in the subtropical southeast Atlantic was driven by interocean exchange south of Africa. The Agulhas transfer strengthened at glacial ice-volume maxima for every glacial-interglacial transition, with maximum reinforcements organized according to a 400-ka periodicity. The long-term dynamics of Agulhas leakage may have played a crucial role in regulating meridional overturning circulation and global climate changes during the Mid-Brunhes event and the Mid-Pleistocene transition, and could also play an important role in the near future.

Aluminium Electroplating on Steel from a Fused Bromide Electrolyte

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prabhat Tripathy; Laura Wurth; Eric Dufek

A quaternary bromide bath (LiBr-KBr-CsBr-AlBr3) was used to electro-coat aluminium on steel substrates. The electrolyte was prepared by the addition of AlBr3 into the eutectic LiBr-KBr-CsBr melt. A smooth, thick, adherent and shiny aluminium coating could be obtained with 80 wt.% AlBr3 in the ternary melt. The SEM photographs of the coated surfaces suggest the formation of thick and dense coatings with good aluminium coverage. Both salt immersion and open circuit potential measurement suggest that the coatings did display good corrosion-resistance behavior. Annealing of the coated surfaces, prior to corrosion tests, suggested the robustness of the metallic aluminium coating inmore » preventing the corrosion of the steel surfaces. Studies also indicated that the quaternary bromide plating bath can potentially provide a better aluminium coating on both ferrous and non-ferrous metals, including complex surfaces/geometries.« less

Syntheses and characterization of novel oxoisoaporphine derivatives as dual inhibitors for cholinesterases and amyloid beta aggregation.

PubMed

Li, Yan-Ping; Ning, Fang-Xian; Yang, Meng-Bi; Li, Yong-Cheng; Nie, Min-Hua; Ou, Tian-Miao; Tan, Jia-Heng; Huang, Shi-Liang; Li, Ding; Gu, Lian-Quan; Huang, Zhi-Shu

2011-05-01

A series of 3-substituted (5c-5f, 6c-6f) and 4-substituted (10a-10g) oxoisoaporphine derivatives were synthesized. It was found that all these synthetic compounds had IC50 values at micro or nano molar range for cholinesterase inhibition, and most of them could inhibit amyloid β (Aβ) self-induced aggregation with inhibition ratio from 31.8% to 57.6%. The structure-activity relationship studies revealed that the derivatives with higher selectivity on AChE also showed better inhibition on Aβ self-induced aggregation. The results from cell toxicity study indicated that most quaternary methiodide salts had higher IC50 values than the corresponding non-quaternary compounds. This study provided potentially important information for further development of oxoisoaporphine derivatives as lead compounds for the treatment of Alzheimer's disease. Copyright © 2011 Elsevier Masson SAS. All rights reserved.

Aliphatic long chain quaternary ammonium compounds analysis by ion-pair chromatography coupled with suppressed conductivity and UV detection in lysing reagents for blood cell analysers.

PubMed

Giovannelli, D; Abballe, F

2005-08-26

A method has been developed which allows simultaneous determination of three linear alkyl trimethylammonium salts. Dodecyltrimethylammonium chloride, tetradecyltrimethylammonium bromide and hexadecyltrimethylammonium chloride are widely used as main active ingredients of lysing reagents for blood cell analyzers which perform white blood cells differential determination into two or more sub-populations by impedance analysis. The ion-pair on styrene-divinyl benzene chromatographic phase looks like a suitable, reliable and long term stable tool for separation of such quaternary compounds. The detection based on suppressed conductivity was chosen because of the lack of significance chromophores. A micromembrane suppressor device compatible with high solvent concentration (up to 80%) was used in order to minimize the conductivity background before the detection. In the present work we show how the chemical post column derivatization makes the alkyl chain detectable also by UV direct detection at 210 nm.

Immunochemical Methods for Quantitation of Vitamin B6

DTIC Science & Technology

1981-09-30

pANk K:E:: Z P a . LIST OF FIGURES Page Figure 1. Synthesis of N-Carboxymethylpyridoxine 15 Figure 2. Pyridoxine and N- Substituted Derivatives 16...Pyridoxine Substituted in the 3 Position 23 Figure 6. Synthesis of as -Pyridoxylformic Acid and as - 25 Pyridoxylacetic Acid Figure 7. Fluorogenic Galactosides...CH20 (Vill) (X Figure 2. Pyridoxine and N- Substituted Derivatives 16 hinder the formation of quaternary salts (Kirpal, 1910).’" We found this to be true

Reaction of azides and enolisable aldehydes under the catalysis of organic bases and Cinchona based quaternary ammonium salts.

PubMed

Destro, Dario; Sanchez, Sandra; Cortigiani, Mauro; Adamo, Mauro F A

2017-06-21

Herein we report a two-step sequence for the preparation of amides starting from azides and enolisable aldehydes. The reaction proceeded via the formation of triazoline intermediates that were converted into amides via Lewis acid catalysis. Preliminary studies on the preparation of triazolines under chiral phase transfer catalysis are also presented, demonstrating that enantioenriched amides could be prepared from achiral aldehydes in moderate to low enantioselectivity.

Novel polymer electrolytes based on cationic polyurethane with different alkyl chain length

NASA Astrophysics Data System (ADS)

Liu, Libin; Wu, Xiwen; Li, Tianduo

2014-03-01

A series of comb-like cationic polyurethanes (PUs) were synthesized by quaternizing different bromoalkane (C2H5Br, C8H17Br, and C14H29Br) with polyurethane. Solid polymer electrolytes were prepared by complexes cationic PUs with different content of LiClO4. All the solid polymer electrolytes had sufficient thermal stability as confirmed by TGA and exhibited a single-phase behavior evidenced by DSC results. For these electrolytes, FT-IR spectra indicated the formation of polymer-ion complexes. The ac impedance spectra show that the conductivity of the electrolytes follow the Arrhenius behavior, and ionic conductivity is associated with both the charge migration of ions between coordination sites and transmission between aggregates, as confirmed by FT-IR and SEM. Alkyl quaternary ammonium salts in the polymer backbone are recognized as inherent plasticizers, which make the electrolytes exhibit liquid-like behavior. The plasticizing effect of PU-C8 and PU-C14 electrolytes are more effective than that of PU-C2 electrolyte. Maximum ionic conductivity at room temperature for PU-C8 electrolytes containing 50 wt% LiClO4 reached 1.1 × 10-4 S cm-1. This work provides a new research clue that alkyl quaternary ammonium salts could be used as inherent plasticizers and hence make the system behave like a liquid with high ionic conductivity, while preserving the dimensional stability of the solids.

CO2 capture from simulated fuel gas mixtures using semiclathrate hydrates formed by quaternary ammonium salts.

PubMed

Park, Sungwon; Lee, Seungmin; Lee, Youngjun; Seo, Yongwon

2013-07-02

In order to investigate the feasibility of semiclathrate hydrate-based precombustion CO2 capture, thermodynamic, kinetic, and spectroscopic studies were undertaken on the semiclathrate hydrates formed from a fuel gas mixture of H2 (60%) + CO2 (40%) in the presence of quaternary ammonium salts (QASs) such as tetra-n-butylammonium bromide (TBAB) and fluoride (TBAF). The inclusion of QASs demonstrated significantly stabilized hydrate dissociation conditions. This effect was greater for TBAF than TBAB. However, due to the presence of dodecahedral cages that are partially filled with water molecules, TBAF showed a relatively lower gas uptake than TBAB. From the stability condition measurements and compositional analyses, it was found that with only one step of semiclathrate hydrate formation with the fuel gas mixture from the IGCC plants, 95% CO2 can be enriched in the semiclathrate hydrate phase at room temperature. The enclathration of both CO2 and H2 in the cages of the QAS semiclathrate hydrates and the structural transition that results from the inclusion of QASs were confirmed through Raman and (1)H NMR measurements. The experimental results obtained in this study provide the physicochemical background required for understanding selective partitioning and distributions of guest gases in the QAS semiclathrate hydrates and for investigating the feasibility of a semiclathrate hydrate-based precombustion CO2 capture process.

Evaluation of Antimicrobial Efficiency of New Polymers Comprised by Covalently Attached and/or Electrostatically Bound Bacteriostatic Species, Based on Quaternary Ammonium Compounds.

PubMed

Kougia, Efstathia; Tselepi, Maria; Vasilopoulos, Gavriil; Lainioti, Georgia Ch; Koromilas, Nikos D; Druvari, Denisa; Bokias, Georgios; Vantarakis, Apostolos; Kallitsis, Joannis K

2015-12-01

In the present work a detailed study of new bacteriostatic copolymers with quaternized ammonium groups introduced in the polymer chain through covalent attachment or electrostatic interaction, was performed. Different copolymers have been considered since beside the active species, the hydrophobic/hydrophilic nature of the co-monomer was also evaluated in the case of covalently attached bacteriostatic groups, aiming at achieving permanent antibacterial activity. Homopolymers with quaternized ammonium/phosphonium groups were also tested for comparison reasons. The antimicrobial activity of the synthesized polymers after 3 and 24 h of exposure at 4 and 22 °C was investigated on cultures of Gram-negative (P. aeruginosa, E. coli) and Gram-positive (S. aureus, E. faecalis) bacteria. It was found that the combination of the hydrophilic monomer acrylic acid (AA), at low contents, with the covalently attached bacteriostatic group vinyl benzyl dimethylhexadecylammonium chloride (VBCHAM) in the copolymer P(AA-co-VBCHAM88), resulted in a high bacteriostatic activity against P. aeruginosa and E. faecalis (6 log reduction in certain cases). Moreover, the combination of covalently attached VBCHAM units with electrostatically bound cetyltrimethylammonium 4-styrene sulfonate (SSAmC16) units in the P(SSAmC16-co-VBCHAMx) copolymers led to efficient antimicrobial materials, especially against Gram-positive bacteria, where a log reduction between 4.9 and 6.2 was verified. These materials remain remarkably efficient even when they are incorporated in polysulfone membranes.

The 87Sr/86Sr ratios of lacustrine carbonates and lake-level history of the Bonneville paleolake system

USGS Publications Warehouse

Hart, W.S.; Quade, Jay; Madsen, D.B.; Kaufman, D.S.; Oviatt, Charles G.

2004-01-01

Lakes in the Bonneville basin have fluctuated dramatically in response to changes in rainfall, temperature, and drainage diversion during the Quaternary. We analyzed tufas and shells from shorelines of known ages in order to develop a relation between 87Sr/86Sr ratio of carbonates and lake level, which then can be used as a basis for constraining lake level from similar analyses on carbonates in cores. Carbonates from the late Quaternary shorelines yield the following average 87Sr/86Sr ratios: 0.71173 for the Stansbury shoreline (22-20 14C ka; 1350 m), 0.71153 for the Bonneville shoreline (15.5-14.5 14C ka; 1550 m), 0.71175 for the Provo shoreline (14.4-14.0 14C ka; 1450 m), 0.71244 for the Gilbert shoreline (???10.3-10.9 14C ka; 1300 m), and 0.71469 for the modern Great Salt Lake (1280 m). These analyses show that the 87Sr/86Sr ratio of lacustrine carbonates changes substantially at low- to mid-lake levels but is invariant at mid- to high-lake levels. Sr-isotope mixing models of Great Salt Lake and the Bonneville paleolake system were constructed to explain these variations in 87Sr/86Sr ratios with change in lake level. Our model of the Bonneville system produced a 87Sr/86Sr ratio of 0.71193, very close to the observed ratios from high-shoreline tufa and shell. The model verifies that the integration of the southern Sevier and Beaver rivers with the Bear and others rivers in the north is responsible for the lower 87Sr/86Sr ratios in Lake Bonneville compared to the modern Great Salt Lake. We also modeled the 87Sr/86Sr ratio of Lake Bonneville with the upper Bear River diverted into the Snake River basin and obtained an 87Sr/86Sr ratio of 0.71414. Coincidentally, this ratio is close to the observed ratio for Great Salt Lake of 0.71469. This means that 87Sr/86Sr ratios of >0.714 for carbonate can be produced by climatically induced low-lake conditions or by diversion of the upper Bear River out of the Bonneville basin. This model result also demonstrates that the upper Bear River had to be flowing into the Bonneville basin during highstands of other late Quaternary lake cycles: carbonates from the Little Valley (130-160 ka) and Cutler Dam (59 ?? 5 ka) lake cycles returned 87Sr/86Sr ratios of 0.71166 and 0.71207, respectively, and are too low to be produced by a lake without the upper Bear River input. ?? 2004 Geological Society of America.

Thermodynamic assessment of the LiF-ThF4-PuF3-UF4 system

NASA Astrophysics Data System (ADS)

Capelli, E.; Beneš, O.; Konings, R. J. M.

2015-07-01

The LiF-ThF4-PuF3-UF4 system is the reference salt mixture considered for the Molten Salt Fast Reactor (MSFR) concept started with PuF3. In order to obtain the complete thermodynamic description of this quaternary system, two binary systems (ThF4-PuF3 and UF4-PuF3) and two ternary systems (LiF-ThF4-PuF3 and LiF-UF4-PuF3) have been assessed for the first time. The similarities between CeF3/PuF3 and ThF4/UF4 compounds have been taken into account for the presented optimization as well as in the experimental measurements performed, which have confirmed the temperatures predicted by the model. Moreover, the experimental results and the thermodynamic database developed have been used to identify potential compositions for the MSFR fuel and to evaluate the influence of partial substitution of ThF4 by UF4 in the salt.

The Corrosion Behavior of Stainless Steel 316L in Novel Quaternary Eutectic Molten Salt System

NASA Astrophysics Data System (ADS)

Wang, Tao; Mantha, Divakar; Reddy, Ramana G.

2017-03-01

In this article, the corrosion behavior of stainless steel 316L in a low melting point novel LiNO3-NaNO3-KNO3-NaNO2 eutectic salt mixture was investigated at 695 K which is considered as thermally stable temperature using electrochemical and isothermal dipping methods. The passive region in the anodic polarization curve indicates the formation of protective oxides layer on the sample surface. After isothermal dipping corrosion experiments, samples were analyzed using SEM and XRD to determine the topography, corrosion products, and scale growth mechanisms. It was found that after long-term immersion in the LiNO3-NaNO3-KNO3-NaNO2 molten salt, LiFeO2, LiFe5O8, Fe3O4, (Fe, Cr)3O4 and (Fe, Ni)3O4 oxides were formed. Among these corrosion products, LiFeO2 formed a dense and protective layer which prevents the SS 316L from severe corrosion.

Morphological and physical behavior of styrenic, phosphonium-containing ionomers

NASA Astrophysics Data System (ADS)

Beyer, Rick; Stokes, Kristoffer

2010-03-01

Despite many years of effort, a clear understanding of the factors controlling morphology in Nafion and other ionomers has not been achieved. The increasing need for fuel cell technology continues to drive efforts to develop materials having better performance characteristics even though fundamental structure-property relationships remain unclarified. Alkaline fuel cells (AFCs) present several benefits over proton exchange membrane (PEM) fuel cells, including cost of manufacture (less expensive catalysts) and a significantly shorter path to commercialization. Here we present the most recent findings from our efforts to examine structure-morphology-property relationships for a series of model cationic ionomers. A series of statistical copolymers of styrene and p-vinylbenzyl-trimethyl-phosphonium chloride have been prepared via RAFT polymerization, allowing us to investigate the effect of ion content on physical behavior. Chemical, physical, and morphological characterization has been undertaken using NMR, TGA, DSC, SAXS, and TEM.

Synthesis of Ionic Liquid Based Electrolytes, Assembly of Li-ion Batteries, and Measurements of Performance at High Temperature.

PubMed

Lin, Xinrong; Chapman Varela, Jennifer; Grinstaff, Mark W

2016-12-20

The chemical instability of the traditional electrolyte remains a safety issue in widely used energy storage devices such as Li-ion batteries. Li-ion batteries for use in devices operating at elevated temperatures require thermally stable and non-flammable electrolytes. Ionic liquids (ILs), which are non-flammable, non-volatile, thermally stable molten salts, are an ideal replacement for flammable and low boiling point organic solvent electrolytes currently used today. We herein describe the procedures to: 1) synthesize mono- and di-phosphonium ionic liquids paired with chloride or bis(trifluoromethane)sulfonimide (TFSI) anions; 2) measure the thermal properties and stability of these ionic liquids by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA); 3) measure the electrochemical properties of the ionic liquids by cyclic voltammetry (CV); 4) prepare electrolytes containing lithium bis(trifluoromethane)sulfonamide; 5) measure the conductivity of the electrolytes as a function of temperature; 6) assemble a coin cell battery with two of the electrolytes along with a Li metal anode and LiCoO2 cathode; and 7) evaluate battery performance at 100 °C. We additionally describe the challenges in execution as well as the insights gained from performing these experiments.

Ultrasonic velocimetry studies on different salts of chitosan: Effect of ion size.

PubMed

Mohan, C Raja; Sathya, R; Nithiananthi, P; Jayakumar, K

2017-11-01

In the present investigation, the effect of ion size on the thermodynamical properties such as ultrasonic velocity (U), adiabatic compressibility (β), acoustic impedance (Z), adiabatic bulk modulus (K s ), relaxation strength (r s ) have been obtained for the different salts of chitosan viz., formate (3.5Å), acetate (4.5Å), Succinate (5Å) and Adipate (6Å). To find the effect of ion size, the effect due to water has been removed by calculating the change in ultrasonic velocity (dU), change in adiabatic compressibility (dβ), in acoustic impedance (dZ), in adiabatic bulk modulus (dK s ), and in relaxation strength (dr s ). Space filling factor and polarizability has been obtained from the refractive index data through Lorentz-Lorentz relation. FTIR studies confirm the formation of different quaternary salts of chitosan and their size (mass) effects which has been verified with Hooke's law. All the said properties vary both with ion size and concentration of different salts of chitosan. This investigation may throw some light on better usage of chitosan in biomedical applications. The detailed results are presented and discussed. Copyright © 2017 Elsevier B.V. All rights reserved.

CO2/pH-Controllable Viscoelastic Nanostructured Fluid Based on Stearic Acid Soap and Bola-Type Quaternary Ammonium Salt.

PubMed

Zhang, Yongmin; Kong, Weiwei; An, Pengyun; He, Shuai; Liu, Xuefeng

2016-03-15

Fatty acid soaps such as sodium stearate (NaOSA) represent a class of cheap, environmentally friendly surfactants; however, their poor solubility seriously challenges their application in various fields. Herein, we describe a CO2/pH-controllable viscoelastic nanostructured fluid, which was developed by simple mixing of the commodity soap NaOSA with a bola-type quaternary ammonium salt (Bola2be) in a 2:1 molar ratio without the need for complex organic synthesis. The introduction of Bola2be increased NaOSA solubility and promoted micelle growth by forming a noncovalent pseudo-Gemini structure, 2NaOSA-Bola2be. Long aggregates are formed with increases in concentration, and these become entangled into a three-dimensional network at 10 times that of the critical micelle concentration (0.057 mM), showing strong thickening ability. Micellar branching occurs above 22.38 mM, as deduced by rheology and verified by cryo-transmission electron microscopy. The worm-based fluid formed from the noncovalent pseudo-Gemini surfactant is highly thermosensitive, and features a higher flow activation energy of 399.76 kJ·mol(-1) compared with common worm systems. Because of the pH-sensitivity of NaOSA, the viscoelastic fluid can respond to common pH stimuli or green CO2 gas, and shows a transition between a gel-like wormlike micellar network and a water-like dispersion with precipitate. However, the CO2-responsive behavior is irreversible.

Trimethylated homoserine functions as the major compatible solute in the globally significant oceanic cyanobacterium Trichodesmium.

PubMed

Pade, Nadin; Michalik, Dirk; Ruth, Wolfgang; Belkin, Natalia; Hess, Wolfgang R; Berman-Frank, Ilana; Hagemann, Martin

2016-11-15

The oceanic N 2 -fixing cyanobacterium Trichodesmium spp. form extensive surface blooms and contribute significantly to marine carbon and nitrogen cycles in the oligotrophic subtropical and tropical oceans. Trichodesmium grows in salinities from 27 to 43 parts per thousand (ppt), yet its salt acclimation strategy remains enigmatic because the genome of Trichodesmium erythraeum strain IMS101 lacks all genes for the biosynthesis of any known compatible solute. Using NMR and liquid chromatography coupled to mass spectroscopy, we identified the main compatible solute in T. erythraeum strain IMS101 as the quaternary ammonium compound N,N,N-trimethyl homoserine (or homoserine betaine) and elucidated its biosynthetic pathway. The identification of this compatible solute explains how Trichodesmium spp. can thrive in the marine system at varying salinities and provides further insight into the diversity of microbial salt acclimation.

Effects of cationic species on visual color formation in model Maillard reactions of pentose sugars and amino acids.

PubMed

Rizzi, George P

2008-08-27

Effects of cationic species on Maillard browning were examined after heating (ca. 100 degrees C) aqueous pH 7.2 buffered solutions of amino acids and pentose sugars. Metallic ions of Group I metals (Li, Na, K, Rb and Cs) produced a small increase in browning (A420), but somewhat greater effects were observed with ions of Group II metals Ca and Mg. Browning was suppressed by triethylammonium ion, but unaffected by a salt of the stronger base, guanidine. The quaternary amine salt choline chloride produced enhanced browning and served as a model for phospholipid involvement in Maillard reactions. With alpha,omega-diamino acids increases in browning were observed which related to lowered pK2 values resulting from positively charged omega-substituents in these molecules.

Rapid fixation of methylene chloride by a macrocyclic amine.

PubMed

Lee, Jung-Jae; Stanger, Keith J; Noll, Bruce C; Gonzalez, Carlos; Marquez, Manuel; Smith, Bradley D

2005-03-30

A simple macrocyclic amine is alkylated by methylene chloride to give a quaternary ammonium chloride salt. When methylene chloride is the solvent, the reaction exhibits pseudo-first-order kinetics, and the reaction half-life at 25.0 degrees C is 2.0 min. The reaction half-life for a structurally related, acyclic amine is approximately 50 000 times longer. Detailed calculations favor a mechanism where the methylene chloride associates with the macrocycle to form an activated prereaction complex. The macrocyclic nitrogen subsequently attacks the methylene chloride with a classic SN2 trajectory, and although the carbon-chlorine bond breaks, the chloride leaving group does not separate from the newly formed cationic macrocycle, such that the product is a tightly associated ion-pair. X-ray crystal structures of the starting amine and the product salt, as well as kinetic data, support this mechanism.

Agulhas leakage as a key process in the modes of Quaternary climate changes

PubMed Central

Caley, Thibaut; Giraudeau, Jacques; Malaizé, Bruno; Rossignol, Linda; Pierre, Catherine

2012-01-01

Heat and salt transfer from the Indian Ocean to the Atlantic Ocean (Agulhas leakage) has an important effect on the global thermohaline circulation and climate. The lack of long transfer record prevents elucidation of its role on climate changes throughout the Quaternary. Here, we present a 1,350-ka accumulation rate record of the planktic foraminiferal species Globorotalia menardii. We demonstrate that, according to previous assumptions, the presence and reseeding of this fauna in the subtropical southeast Atlantic was driven by interocean exchange south of Africa. The Agulhas transfer strengthened at glacial ice-volume maxima for every glacial-interglacial transition, with maximum reinforcements organized according to a 400-ka periodicity. The long-term dynamics of Agulhas leakage may have played a crucial role in regulating meridional overturning circulation and global climate changes during the Mid-Brunhes event and the Mid-Pleistocene transition, and could also play an important role in the near future. PMID:22508999

Quaternary geology of the Rhode Island inner shelf

USGS Publications Warehouse

Needell, S. W.; O'Hara, C. J.; Knebel, H.J.

1983-01-01

Five sedimentary units and three erosional unconformities identified in high-resolution seismic-reflection profiles reveal the stratigraphic framework and Quaternary history of the inner continental shelf south of Narragansett Bay, Rhode Island. Late Tertiary to early Pleistocene rivers eroded the pre-Mesozoic bedrock and the Upper Cretaceous to lower Tertiary coastal plain and continental shelf strata to form a lowland and cuesta having a north-facing escarpment. The lowland and landward flanks of the cuesta were modified by glaciers during Pleistocene time and subsequently were overlain by drift and end moraine deposits of the late Wisconsinan ice advance. During deglaciation, freshwater lakes formed between the retreating ice and end moraines. Prior to sea-level rise, the drift and older deposits were cut by streams flowing south and southwestward toward Block Island Sound. As sea level rose, postglacial valleys were partly filled by fluvial, freshwater-peat, estuarine and salt-marsh deposits. Transgressing seas eroded the sea floor, exposing bedrock and coastal plain outcrops, and deposited marine sediments. ?? 1983.

Synthesis of Water-Soluble Amino Functionalized Multithiacalix[4]arene via Quaternization of Tertiary Amino Groups.

PubMed

Nosov, Roman; Padnya, Pavel; Shurpik, Dmitriy; Stoikov, Ivan

2018-05-08

A convenient approach to the synthesis of multithiacalix[4]arene derivatives containing amino groups and phthalimide fragments by the formation of quaternary ammonium salts is presented. As the initial macrocycle for the synthesis of multithiacalix[4]arenes, a differently substituted p-tert- butylthiacalix[4]arene containing bromoacetamide and three phthalimide fragments was used in a 1,3-alternate conformation. The macrocycle in cone conformation containing the tertiary amino groups was found to be a convenient core for the multithiacalix[4]arene systems. Interaction of the core multithiacalix[4]arene with monobromoacetamide derivatives of p-tert- butylthiacalix[4]arene resulted in formation in high yields of pentakisthiacalix[4]arene containing quaternary ammonium and phthalimide fragments. The removal of phthalimide groups led to the formation of amino multithiacalix[4]arene in a good yield. Based on dynamic light scattering, it was shown that the synthesized amino multithiacalix[4]arene, with pronounced hydrophobic and hydrophilic fragments, formed dendrimer-like nanoparticles in water via direct supramolecular self-assembly.

Effect of ionic liquids on the interaction between liposomes and common wastewater pollutants investigated by capillary electrophoresis.

PubMed

Ruokonen, Suvi-Katriina; Duša, Filip; Lokajová, Jana; Kilpeläinen, Ilkka; King, Alistair W T; Wiedmer, Susanne K

2015-07-31

The effect of three phosphonium and imidazolium ionic liquids (ILs) on the interaction between liposomes and common pharmaceuticals found in wastewaters was studied. The liposomes comprised zwitterionic phosphatidyl choline and negatively charged phosphatidyl glycerol. A set of common cationic, anionic, and neutral compounds with varying chemical composition and unique structures were included in the study. The electrophoretic mobilities of the analytes were determined using conventional capillary electrophoresis (CE), using CE under reversed electroosmotic flow mobility conditions, and in the presence of ILs in the background electrolyte (BGE) solution by electrokinetic chromatography (EKC). In order to evaluate the impact of ILs on the interaction between the compounds and the liposomes, EKC was performed with liposome dispersions, with and without ILs. The retention factors of the compounds were calculated using BGEs including liposome dispersions with and without ILs. Two phosphonium based ILs, namely tributyl(tetradecyl)phosphonium chloride ([P14444]Cl) and octyltributylphosphonium chloride ([P8444]Cl), were chosen due to their long alkyl chains and their low aggregation concentrations. Another IL, i.e. 1-ethyl-3-methylimidazolium acetate ([emim][OAc]), was chosen based on our previous study, which suggests that it has a minimal or even nonexistent effect on liposomes at the used concentrations. The results indicate that the studied ILs have an effect on the interactions between wastewater compounds and liposomes, but the effect is highly dependent on the concentration of the IL and on the IL alkyl chain lengths. Most of the ILs hindered the interactions between the liposomes and the compounds, indicating strong interaction between ILs and liposomes. In addition, the nature of the studied compounds themselves affected the interactions. Copyright © 2015 Elsevier B.V. All rights reserved.

Electroreduction of Er 3+ in nonaqueous solvents

DOE PAGES

Small, Leo J.; Sears, Jeremiah M.; Lambert, Timothy N.; ...

2016-09-15

Here, the electroreduction of Er 3+ in propylene carbonate, N,N-dimethylformamide, or a variety of quaternary ammonium ionic liquids (ILs) was investigated using [Er(OTf) 3] and [Er(NTf 2) 3]. Systematic variation of the ILs' cation and anion, Er 3+ salt, and electrode material revealed a disparity in electrochemical interactions not previously seen. For most ILs at a platinum electrode, cyclic voltammetry exhibits irreversible interactions between Er 3+ salts and the electrode at potentials significantly less than the theoretical reduction potential for Er 3+. Throughout all solvent–salt systems tested, a deposit could be formed on the electrode, though obtaining a high purity,more » crystalline Er 0 deposit is challenging due to the extreme reactivity of the deposit and resulting chemical interactions, often resulting in the formation of a complex, amorphous solid–electrolyte interface that slowed deposition rates. Comparison of platinum, gold, nickel, and glassy carbon (GC) working electrodes revealed oxidation processes unique to the platinum surface. While no appreciable reduction current was observed on GC at the potentials investigated, deposits were seen on platinum, gold, and nickel electrodes.« less

Electrochemical device for converting carbon dioxide to a reaction product

DOE Office of Scientific and Technical Information (OSTI.GOV)

Masel, Richard I.; Chen, Qingmei; Liu, Zengcai

An electrochemical device converts carbon dioxide to a reaction product. The device includes an anode and a cathode, each comprising a quantity of catalyst. The anode and cathode each has reactant introduced thereto. A polymer electrolyte membrane is interposed between the anode and the cathode. At least a portion of the cathode catalyst is directly exposed to gaseous carbon dioxide during electrolysis. The average current density at the membrane is at least 20 mA/cm.sup.2, measured as the area of the cathode gas diffusion layer that is covered by catalyst, and CO selectivity is at least 50% at a cell potentialmore » of 3.0 V. In some embodiments, the polymer electrolyte membrane comprises a polymer in which a constituent monomer is (p-vinylbenzyl)-R, where R is selected from the group consisting of imidazoliums, pyridiniums and phosphoniums. In some embodiments, the polymer electrolyte membrane is a Helper Membrane comprising a polymer containing an imidazolium ligand, a pyridinium ligand, or a phosphonium ligand.« less

A Tunable and Enantioselective Hetero-Diels-Alder Reaction Provides Access to Distinct Piperidinoyl Spirooxindoles.

PubMed

Jayakumar, Samydurai; Louven, Kathrin; Strohmann, Carsten; Kumar, Kamal

2017-12-11

The active complexes of chiral N,N'-dioxide ligands with dysprosium and magnesium salts catalyze the hetero-Diels-Alder reaction between 2-aza-3-silyloxy-butadienes and alkylidene oxindoles to selectively form 3,3'- and 3,4'-piperidinoyl spirooxindoles, respectively, in very high yields and with excellent enantioselectivities. The exo-selective asymmetric cycloaddition successfully regaled the construction of sp 3 -rich and highly substituted natural-product-based spirooxindoles supporting many chiral centers, including contiguous all-carbon quaternary centers. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrolytes For Electrooptic Devices Comprising Ionic Liqu Ids

DOEpatents

Warner, Benjamin P.; McCleskey, T. Mark; Agrawal, Anoop; Cronin, John P.; Tonazzi, Juan C. L.; Burrell, Anthony K.

2005-02-08

Electrolyte solutions of soluble bifunctional redox dyes in molten salt solvent may be used to prepare electrooptic devices with enhanced stability toward ultraviolet radiation. The solvents include lithium or quaternary ammonium cations, and perfluorinated sulfonylimide anions selected from trifluoromethylsulfonate (CF.sub.3 SO.sub.3.sup.-), bis(trifluoromethylsulfonyl)imide ((CF.sub.3 SO.sub.2).sub.2 N.sup.-), bis(perfluoroethylsulfonyl)imide ((CF.sub.3 CF.sub.2 SO.sub.2).sub.2 N.sup.-) and tris(trifluoromethylsulfonyl)methide ((CF.sub.3 SO.sub.2).sub.3 C.sup.-).

Ice-load induced tectonics controlled tunnel valley evolution - instances from the southwestern Baltic Sea

NASA Astrophysics Data System (ADS)

Al Hseinat, M.; Hübscher, C.

2014-08-01

Advancing ice sheets have a strong impact on the earth's topography. For example, they leave behind an erosional unconformity, bulldozer the underlying strata and form tunnel valleys, primarily by subglacial melt-water erosion and secondarily by direct glacial erosion. The conceptual models of the reactivation of faults within the upper crust, due to the ice sheets' load, are also established. However, this phenomenon is also rather under-explored. Here, we propose a causal link between ice-load induced tectonics, the generation of near-vertical faults in the upper crust above an inherited deep-rooted fault and the evolution of tunnel valleys. The Kossau tunnel valley in the southeastern Bay of Kiel has been surveyed by means of high-resolution multi-channel seismic and echosounder data. It strikes almost south to north and can be mapped over a distance of ca 50 km. It is 1200-8000 m wide with a valley of up to 200 m deep. Quaternary deposits fill the valley and cover the adjacent glaciogenic unconformity. A near-vertical fault system with an apparent dip angle of >80°, which reaches from the top Zechstein upwards into the Quaternary, underlies the valley. The fault partially pierces the seafloor and growth is observed within the uppermost Quaternary strata only. Consequently, the fault evolved in the Late Quaternary. The fault is associated with an anticline that is between 700 and 3000 m wide and about 20-40 m high. The fault-anticline assemblage neither resembles any typical extensional, compressional or strike-slip deformation pattern, nor is it related to salt tectonics. Based on the observed position and deformation pattern of the fault-anticline assemblage, we suggest that these structures formed as a consequence of the differential ice-load induced tectonics above an inherited deep-rooted sub-salt fault related to the Glückstadt Graben. Lateral variations in the ice-load during the ice sheet's advance caused differential subsidence, thus rejuvenating the deep-rooted fault. As a result, the inherited fault propagated upwards across the Zechstein and post-Permian overburden and further grew during the ice sheet's retreat. The developing fault and anticline system under the ice sheet created a weakness zone that facilitated erosion by pressurized glacial and subglacial melt-water, as well as by the glaciers themselves. Near-vertical faults cutting through the post-Permian are abundant in the southwestern Baltic realm, which implies that the ice-load induced tectonic activity described above was not an isolated incident.

Phylogeography in Galaxias maculatus (Jenyns, 1848) along Two Biogeographical Provinces in the Chilean Coast

PubMed Central

González-Wevar, Claudio A.; Salinas, Pilar; Hüne, Mathias; Segovia, Nicolás I.; Vargas-Chacoff, Luis; Astorga, Marcela; Cañete, Juan I.; Poulin, Elie

2015-01-01

Major geologic and climatic changes during the Quaternary exerted a major role in shaping past and contemporary distribution of genetic diversity and structure of aquatic organisms in southern South America. In fact, the northern glacial limit along the Pacific coast, an area of major environmental changes in terms of topography, currents, and water salinity, represents a major biogeographic transition for marine and freshwater species. We used mitochondrial DNA sequences (D-loop) to investigate the consequences of Quaternary glacial cycles over the pattern of genetic diversity and structure of G. maculatus (Pisces: Galaxiidae) along two biogeographical provinces in the Chilean coast. Extreme levels of genetic diversity and strong phylogeographic structure characterize the species suggesting a low amount of influence of the last glacial cycle over its demography. However, we recognized contrasting patterns of genetic diversity and structure between main biogeographical areas here analyzed. Along the Intermediate Area (38°–41° S) each estuarine population constitutes a different unit. In contrast, Magellanic populations (43°–53° S) exhibited low levels of genetic differentiation. Contrasting patterns of genetic diversity and structure recorded in the species between the analyzed biogeographic areas are consistent with the marked differences in abiotic factors (i.e., different coastal configurations, Quaternary glacial histories, and oceanographic regimes) and to inherent characteristics of the species (i.e., salt-tolerance, physiology, and reproductive behavior). PMID:26161896

Drifting propagules and receding swamps: genetic footprints of mangrove recolonization and dispersal along tropical coasts.

PubMed

Nettel, Alejandro; Dodd, Richard S

2007-04-01

Two issues that have captured the attention of tropical plant evolutionary biologists in recent years are the relative role of long distance dispersal (LDD) over vicariance in determining plant distributions and debate about the extent that Quaternary climatic changes affected tropical species. Propagules of some mangrove species are assumed to be capable of LDD due to their ability to float and survive for long periods of time in salt water. Mangrove species responded to glaciations with a contraction of their range. Thus, widespread mangrove species are an ideal system to study LDD and recolonization in the tropics. We present phylogenetic and phylogeographic analyses based on internal transcribed spacers region (ITS) sequences, chloroplast DNA (cpDNA), and amplified fragment length polymorphisms (AFLPs) of genomic DNA that demonstrate recent LDD across the Atlantic, rejecting the hypothesis of vicariance for the widespread distribution of the black mangrove (Avicennia germinans). Northern latitude populations likely became extinct during the late Quaternary due to frosts and aridification; these locations were recolonized afterward from southern populations. In some low latitude regions populations went extinct or were drastically reduced during the Quaternary because of lack of suitable habitat as sea levels changed. Our analyses show that low latitude Pacific populations of A. germinans harbor more diversity and reveal deeper divergence than Atlantic populations. Implications for our understanding of phylogeography of tropical species are discussed.

Quaternary bedrock erosion and landscape evolution in the Sør Rondane Mountains, East Antarctica: Reevaluating rates and processes

NASA Astrophysics Data System (ADS)

Matsuoka, Norikazu; Thomachot, Céline E.; Oguchi, Chiaki T.; Hatta, Tamao; Abe, Masahiro; Matsuzaki, Hiroyuki

2006-11-01

Rates and processes of rock weathering, soil formation, and mountain erosion during the Quaternary were evaluated in an inland Antarctic cold desert. The fieldwork involved investigations of weathering features and soil profiles for different stages after deglaciation. Laboratory analyses addressed chemistry of rock coatings and soils, as well as 10Be and 26Al exposure ages of the bedrock. Less resistant gneiss bedrock exposed over 1 Ma shows stone pavements underlain by in situ produced silty soils thinner than 40 cm and rich in sulfates, which reflect the active layer thickness, the absence of cryoturbation, and the predominance of salt weathering. During the same exposure period, more resistant granite bedrock has undergone long-lasting cavernous weathering that produces rootless mushroom-like boulders with a strongly Fe-oxidized coating. The red coating protects the upper surface from weathering while very slow microcracking progresses by the growth of sulfates. Geomorphological evidence and cosmogenic exposure ages combine to provide contrasting average erosion rates. No erosion during the Quaternary is suggested by a striated roche moutonnée exposed more than 2 Ma ago. Differential erosion between granite and gneiss suggests a significant lowering rate of desert pavements in excess of 10 m Ma - 1 . The landscape has been (on the whole) stable, but the erosion rate varies spatially according to microclimate, geology, and surface composition.

Experimental determination of water activity for binary aqueous cerium(III) ionic solutions: application to an assessment of the predictive capability of the binding mean spherical approximation model.

PubMed

Ruas, Alexandre; Simonin, Jean-Pierre; Turq, Pierre; Moisy, Philippe

2005-12-08

This work is aimed at a description of the thermodynamic properties of actinide salt solutions at high concentration. The predictive capability of the binding mean spherical approximation (BIMSA) theory to describe the thermodynamic properties of electrolytes is assessed in the case of aqueous solutions of lanthanide(III) nitrate and chloride salts. Osmotic coefficients of cerium(III) nitrate and chloride were calculated from other lanthanide(III) salts properties. In parallel, concentrated binary solutions of cerium nitrate were prepared in order to measure experimentally its water activity and density as a function of concentration, at 25 degrees C. Water activities of several binary solutions of cerium chloride were also measured to check existing data on this salt. Then, the properties of cerium chloride and cerium nitrate solutions were compared within the BIMSA model. Osmotic coefficient values for promethium nitrate and promethium chloride given by this theory are proposed. Finally, water activity measurements were made to examine the fact that the ternary system Ce(NO3)3/HNO3/H2O and the quaternary system Ce(NO3)3/HNO3/N2H5NO3/H2O may be regarded as "simple solutions" (in the sense of Zdanovskii and Mikulin).

Headspace gas chromatography based methodology for the analysis of aromatic substituted quaternary ammonium salts.

PubMed

van Boxtel, Niels; Wolfs, Kris; Palacín, Marta Guillén; Van Schepdael, Ann; Adams, Erwin

2016-12-09

The analysis of quaternary ammonium salts (QAS) using GC is often performed by "in injector" pyrolysis to create volatile degradation products for quantification purposes. Besides the risk of severe system contamination, the application of this approach on aqueous samples is problematic. In this work, the sample is treated in a vial with 2,2-dimethoxypropane (DMP) under acidic catalysis. In addition to the removal of water and sample enrichment, the QAS are decomposed. As HS transfers only volatile compounds to the GC system, contamination is avoided. It was found that depending on the presence of benzyl, phenyl or methyl groups on the quaternary nitrogen; benzyl chloride, N,N-dimethylaniline or chloromethane are formed respectively in the sealed vial. All these can be used as an analytical target. A calibration curve for benzyl chloride could be derived from the pure compound. Chloromethane was generated from pure benzyldimethyldecylammonium chloride (BEDIDE), a pure QAS with benzyl and methyl groups, to construct a secondary calibration curve using a back analysis approach. It has been proven that by quantifying the formed analytical targets, the mass balance for the QAS under investigation was close to 100%. The presented procedure allows the quantification of any aromatic substituted QAS without the need for a matching reference, which is a major advantage over existing CE and LC methods The proposed methodology was validated for mouth sprays containing benzethonium chloride (BZTCl) or benzoxonium chloride (BZOCl) and for denatonium benzoate (DB) in ethylene glycol (EG) based cooling liquids. Results showed that the approach provided excellent linearity (R 2 ≥0.999) and limits of detection around 0.01μg/vial for benzyl chloride. It was found that the reaction product of DMP and glycerol which was also present in the mouthspray and some cooling liquids, caused chromatographic interference with benzyl chloride. Treating those samples in the vial with N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) after the enrichment step removes the interference and leaves a possible pathway for the simultaneous determination of glycerol in those samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Synthesis and thermo-physical properties of deep eutectic solvent-based graphene nanofluids

NASA Astrophysics Data System (ADS)

Fang, Y. K.; Osama, M.; Rashmi, W.; Shahbaz, K.; Khalid, M.; Mjalli, F. S.; Farid, M. M.

2016-02-01

This study introduces a new class of heat transfer fluids by dispersing functionalised graphene oxide nanoparticles (GNPs) in ammonium and phosphonium-based deep eutectic solvents (DESs) without the aid of a surfactant. Different molar ratios of salts and hydrogen bond donors (HBD) were used to synthesise DESs for the preparation of different concentrations of graphene nanofluids (GNFs). The concentrations of GNPs were 0.01 wt%, 0.02 wt% and 0.05 wt %. Homogeneous and stable suspensions of nanofluids were obtained by high speed homogenisation and an ultrasonication process. The stability of the GNFs was determined through visual observation for 4 weeks followed by a centrifugal process (5000-20 000 rpm) for 30 min in addition to zeta potential studies. Dispersion of the GNPs in DES was observed using an optical microscope. The synthesised DES-based GNFs showed no particle agglomeration and formation of sediments in the nanofluids. Thermo-physical properties such as thermal conductivity and specific heat of the nanofluids were also investigated in this research. The highest thermal conductivity enhancement of 177% was observed. The findings of this research provide a new class of engineered fluid for heat transfer applications as a function of temperature, type and composition DESs as well as the GNPs concentration.

Synthesis and thermo-physical properties of deep eutectic solvent-based graphene nanofluids.

PubMed

Fang, Y K; Osama, M; Rashmi, W; Shahbaz, K; Khalid, M; Mjalli, F S; Farid, M M

2016-02-19

This study introduces a new class of heat transfer fluids by dispersing functionalised graphene oxide nanoparticles (GNPs) in ammonium and phosphonium-based deep eutectic solvents (DESs) without the aid of a surfactant. Different molar ratios of salts and hydrogen bond donors (HBD) were used to synthesise DESs for the preparation of different concentrations of graphene nanofluids (GNFs). The concentrations of GNPs were 0.01 wt%, 0.02 wt% and 0.05 wt %. Homogeneous and stable suspensions of nanofluids were obtained by high speed homogenisation and an ultrasonication process. The stability of the GNFs was determined through visual observation for 4 weeks followed by a centrifugal process (5000-20,000 rpm) for 30 min in addition to zeta potential studies. Dispersion of the GNPs in DES was observed using an optical microscope. The synthesised DES-based GNFs showed no particle agglomeration and formation of sediments in the nanofluids. Thermo-physical properties such as thermal conductivity and specific heat of the nanofluids were also investigated in this research. The highest thermal conductivity enhancement of 177% was observed. The findings of this research provide a new class of engineered fluid for heat transfer applications as a function of temperature, type and composition DESs as well as the GNPs concentration.

Characterization and bioactivity of novel calcium antagonists - N-methoxy-benzyl haloperidol quaternary ammonium salt

PubMed Central

Chen, Yi-Cun; Zhu, Wei; Zhong, Shu-Ping; Zheng, Fu-Chun; Gao, Fen-Fei; Zhang, Yan-Mei; Xu, Han; Zheng, Yan-Shan; Shi, Gang-Gang

2015-01-01

BACKGROUND AND PURPOSE Calcium antagonists play an important role in clinical practice. However, most of them have serious side effects. We have synthesized a series of novel calcium antagonists, quaternary ammonium salt derivatives of haloperidol with N-p-methoxybenzyl (X1), N-m-methoxybenzyl (X2) and N-o-methoxybenzyl (X3) groups. The objective of this study was to investigate the bioactivity of these novel calcium antagonists, especially the vasodilation activity and cardiac side-effects. The possible working mechanisms of these haloperidol derivatives were also explored. EXPERIMENTAL APPROACH Novel calcium antagonists were synthesized by amination. Compounds were screened for their activity of vasodilation on isolated thoracic aortic ring of rats. Their cardiac side effects were explored. The patch-clamp, confocal laser microscopy and the computer-fitting molecular docking experiments were employed to investigate the possible working mechanisms of these calcium antagonists. RESULTS The novel calcium antagonists, X1, X2 and X3 showed stronger vasodilation effect and less cardiac side effect than that of classical calcium antagonists. They blocked L-type calcium channels with an potent effect order of X1 > X2 > X3. Consistently, X1, X2 and X3 interacted with different regions of Ca2+-CaM-CaV1.2 with an affinity order of X1 > X2 > X3. CONCLUSIONS The new halopedidol derivatives X1, X2 and X3 are novel calcium antagonists with stronger vasodilation effect and less cardiac side effect. They could have wide clinical application. PMID:26544729

Comparing effectiveness of rhamnolipid biosurfactant with a quaternary ammonium salt surfactant for hydrate anti-agglomeration.

PubMed

York, J Dalton; Firoozabadi, Abbas

2008-01-24

Natural gas is projected to be the premium fuel of the 21st century because of availability, as well as economical and environmental considerations. Natural gas is coproduced with water from the subsurface forming gas hydrates. Hydrate formation may result in shutdown of onshore and offshore operations. Industry practice has been usage of alcohols--which have undesirable environmental impacts--to affect bulk-phase properties and inhibit hydrate formation. An alternative to alcohols is changing the surface properties through usage of polymers and surfactants, effective at 0.5-3 wt % of coproduced water. One group of low-dosage hydrate inhibitors (LDHI) are kinetic inhibitors, which affect nucleation rate and growth. A second group of LDHI are anti-agglomerants, which prevent agglomeration of small hydrate crystallites. Despite great potential, reported work on hydrate anti-agglomeration is very limited. In this paper, our focus is on the use of two vastly different surfactants as anti-agglomerants. We use a model oil, water, and tetrahydrofuran as a hydrate-forming species. We examine the effectiveness of a quaternary ammonium salt (i.e., quat). Visual observation measurements show that a small concentration of the quat (0.01%) can prevent agglomeration. However, a quat is not a green chemical and therefore may be undesirable. We show that a rhamnolipid biosurfactant can be effective to a concentration of 0.05 wt %. One difference between the two surfactants is the stability of the water-in-oil emulsions created. The biosurfactant forms a less stable emulsion, which makes it very desirable for hydrate application.

Electrochemical membrane incinerator

DOEpatents

Johnson, Dennis C.; Houk, Linda L.; Feng, Jianren

2001-03-20

Electrochemical incineration of p-benzoquinone was evaluated as a model for the mineralization of carbon in toxic aromatic compounds. A Ti or Pt anode was coated with a film of the oxides of Ti, Ru, Sn and Sb. This quaternary metal oxide film was stable; elemental analysis of the electrolyzed solution indicated the concentration of these metal ions to be 3 .mu.g/L or less. The anode showed good reactivity for the electrochemical incineration of benzoquinone. The use of a dissolved salt matrix as the so-called "supporting electrolyte" was eliminated in favor of a solid-state electrolyte sandwiched between the anode and cathode.

Durable electrooptic devices comprising ionic liquids

DOEpatents

Agrawal, Anoop; Cronin, John P.; Tonazzi, Juan C. L.; Warner, Benjamin P.; McCleskey, T. Mark; Burrell, Anthony K.

2005-11-01

Electrolyte solutions for electrochromic devices such as rear view mirrors and displays with low leakage currents are prepared using inexpensive, low conductivity conductors. Preferred electrolytes include bifunctional redox dyes and molten salt solvents with enhanced stability toward ultraviolet radiation. The solvents include lithium or quaternary ammonium cations, and perfluorinated sulfonylimide anions selected from trifluoromethylsulfonate (CF3SO3-), bis(trifluoromethylsulfonyl)imide ((CF3SO2)2N-), bis(perfluoroethylsulfonyl)imide ((CF3CF2SO2)2N-) and tris(trifluoromethylsulfonyl)methide ((CF3SO2)3C-). Electroluminescent, electrochromic and photoelectrochromic devices with nanostructured electrodes include ionic liquids with bifunctional redox dyes.

Allyl triphenyl phosphonium bromide based DES-functionalized carbon nanotubes for the removal of mercury from water.

PubMed

AlOmar, Mohamed Khalid; Alsaadi, Mohammed Abdulhakim; Hayyan, Maan; Akib, Shatirah; Ibrahim, Muhammad; Hashim, Mohd Ali

2017-01-01

Recently, deep eutectic solvents (DESs) have shown their new and interesting ability for chemistry through their involvement in variety of applications. This study introduces carbon nanotubes (CNTs) functionalized with DES as a novel adsorbent for Hg 2+ from water. Allyl triphenyl phosphonium bromide (ATPB) was combined with glycerol as the hydrogen bond donor (HBD) to form DES, which can act as a novel CNTs functionalization agent. The novel adsorbent was characterized using Raman, FTIR, XRD, FESEM, EDX, BET surface area, TGA, TEM and Zeta potential. Response surface methodology was used to optimize the removal conditions for Hg 2+ . The optimum removal conditions were found to be pH 5.5, contact time 28 min, and an adsorbent dosage of 5 mg. Freundlich isotherm model described the adsorption isotherm of the novel adsorbent, and the maximum adsorption capacity obtained from the experimental data was 186.97 mg g -1 . Pseudo-second order kinetics describes the adsorption rate order. Copyright © 2016 Elsevier Ltd. All rights reserved.

Inorganic selenium speciation analysis in Allium and Brassica vegetables by ionic liquid assisted liquid-liquid microextraction with multivariate optimization.

PubMed

Castro Grijalba, Alexander; Martinis, Estefanía M; Wuilloud, Rodolfo G

2017-03-15

A highly sensitive vortex assisted liquid-liquid microextraction (VA-LLME) method was developed for inorganic Se [Se(IV) and Se(VI)] speciation analysis in Allium and Brassica vegetables. Trihexyl(tetradecyl)phosphonium decanoate phosphonium ionic liquid (IL) was applied for the extraction of Se(IV)-ammonium pyrrolidine dithiocarbamate (APDC) complex followed by Se determination with electrothermal atomic absorption spectrometry. A complete optimization of the graphite furnace temperature program was developed for accurate determination of Se in the IL-enriched extracts and multivariate statistical optimization was performed to define the conditions for the highest extraction efficiency. Significant factors of IL-VA-LLME method were sample volume, extraction pH, extraction time and APDC concentration. High extraction efficiency (90%), a 100-fold preconcentration factor and a detection limit of 5.0ng/L were achieved. The high sensitivity obtained with preconcentration and the non-chromatographic separation of inorganic Se species in complex matrix samples such as garlic, onion, leek, broccoli and cauliflower, are the main advantages of IL-VA-LLME. Copyright © 2016 Elsevier Ltd. All rights reserved.

Enhancing sludge biodegradability and volatile fatty acid production by tetrakis hydroxymethyl phosphonium sulfate pretreatment.

PubMed

Wu, Qing-Lian; Guo, Wan-Qian; Bao, Xian; Yin, Ren-Li; Feng, Xiao-Chi; Zheng, He-Shan; Luo, Hai-Chao; Ren, Nan-Qi

2017-09-01

A new pretreatment method based on tetrakis hydroxymethyl phosphonium sulfate (THPS) biocide was tried to enhance sludge disintegration, and improved sludge biodegradability and subsequent volatile fatty acid (VFA) production. Sludge activity decreased to less than 10% after 2 days pretreatment using 20mg/g-TSS THPS, which also obviously destroyed EPS and cell membrane, and dissolved more biodegradable substances (48.8%) than raw sludge (19.7%). Moreover, 20mg/g-TSS THPS pretreatment shortened fermentation time to 4days and improved VFA production to 2778mg COD/L (4.35 times than that in control). Therein, the sum of n-butyric, n-valeric and iso-valeric acids unexpectedly accounted for 60.5% of total VFA (only 20.1% of that in control). The more high molecular weight VFAs (C4-C5) than low molecular VFAs (C2-C3) resulted from THPS pretreatment benefited to subsequent medium-chain volatile acids (C6-C12) generation to realize the separation and recovery of organic carbon more efficiently. Copyright © 2017. Published by Elsevier Ltd.

Extraction and Esterification of Low-Titer Short-Chain Volatile Fatty Acids from Anaerobic Fermentation with Ionic Liquids.

PubMed

Andersen, Stephen J; Berton, Jan K E T; Naert, Pieter; Gildemyn, Sylvia; Rabaey, Korneel; Stevens, Christian V

2016-08-23

Ionic liquids can both act as a solvent and mediate esterification to valorize low-titer volatile fatty acids and generate organic solvents from renewable carbon sources including biowaste and CO2 . In this study, four phosphonium ionic liquids were tested for single-stage extraction of acetic acid from a dilute stream and esterification to ethyl acetate with added ethanol and heat. The esterification proceeded with a maximum conversion of 85.9±1.3 % after 30 min at 75 °C at a 1:1 stoichiometric ratio of reactants. Extraction and esterification can be tailored using mixed-anion ionic liquids; this is demonstrated herein using a common trihexyl(tetradecyl)phosphonium cation and a mixed chloride and bis(trifluoromethylsulfonyl)imide anion ionic liquid. As a further proof-of-concept, ethyl acetate was generated from an ionic liquid-driven esterification of an acetic acid extractant generated using CO2 as the only carbon source by microbial electrosynthesis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanostructured Silica/Gold-Cellulose-Bonded Amino-POSS Hybrid Composite via Sol-Gel Process and Its Properties.

PubMed

Ramesh, Sivalingam; Kim, Heung Soo; Lee, Young-Jun; Hong, Gwang-Wook; Kim, Joo-Hyung

2017-12-01

It is demonstrated in this paper that silica nanoparticles coated with core/shell gold provide efficient thermal, optical, and morphological properties with respect to the cellulose-polyhedral oligomeric silsesquioxanes (POSS) hybrid system. The one-step synthesis of a silica/gold nanocomposite is achieved with a simultaneous hydrolysis and reduction of gold chloride in the presence of formic acid, and the trimethoxysilane group acts as a silica precursor. The focus here comprises the synthesis of cellulose-POSS and silica/gold hybrid nanocomposites using the following two methods: (1) an in situ sol-gel process and (2) a polyvinyl alcohol/tetrakis (hydroxymethyl)phosphonium chloride process. Accordingly, the silica/gold core/shell nanoparticles are synthesized. The growth and attachment of the gold nanoparticles onto the functionalized surface of the silica at the nanometer scale is achieved via both the sol-gel and the tetrakis (hydroxymethyl) phosphonium chloride processes. The cellulose-POSS-silica/gold nanocomposites are characterized according to Fourier transformed infrared spectroscopy, Raman, X-ray diffraction, UV, photoluminescence, SEM, energy-dispersive X-ray spectroscopy, TEM, thermogravimetric, and Brunauer-Emmett-Teller analyses.

Nanostructured Silica/Gold-Cellulose-Bonded Amino-POSS Hybrid Composite via Sol-Gel Process and Its Properties

NASA Astrophysics Data System (ADS)

Ramesh, Sivalingam; Kim, Heung Soo; Lee, Young-June; Hong, Gwang-Wook; Kim, Joo-Hyung

2017-06-01

It is demonstrated in this paper that silica nanoparticles coated with core/shell gold provide efficient thermal, optical, and morphological properties with respect to the cellulose-polyhedral oligomeric silsesquioxanes (POSS) hybrid system. The one-step synthesis of a silica/gold nanocomposite is achieved with a simultaneous hydrolysis and reduction of gold chloride in the presence of formic acid, and the trimethoxysilane group acts as a silica precursor. The focus here comprises the synthesis of cellulose-POSS and silica/gold hybrid nanocomposites using the following two methods: (1) an in situ sol-gel process and (2) a polyvinyl alcohol/tetrakis (hydroxymethyl)phosphonium chloride process. Accordingly, the silica/gold core/shell nanoparticles are synthesized. The growth and attachment of the gold nanoparticles onto the functionalized surface of the silica at the nanometer scale is achieved via both the sol-gel and the tetrakis (hydroxymethyl) phosphonium chloride processes. The cellulose-POSS-silica/gold nanocomposites are characterized according to Fourier transformed infrared spectroscopy, Raman, X-ray diffraction, UV, photoluminescence, SEM, energy-dispersive X-ray spectroscopy, TEM, thermogravimetric, and Brunauer-Emmett-Teller analyses.

Peptoids: a modular approach to drug discovery.

PubMed Central

Simon, R J; Kania, R S; Zuckermann, R N; Huebner, V D; Jewell, D A; Banville, S; Ng, S; Wang, L; Rosenberg, S; Marlowe, C K

1992-01-01

Peptoids, oligomers of N-substituted glycines, are described as a motif for the generation of chemically diverse libraries of novel molecules. Ramachandran-type plots were calculated and indicate a greater diversity of conformational states available for peptoids than for peptides. The monomers incorporate t-butyl-based side-chain and 9-fluorenylmethoxy-carbonyl alpha-amine protection. The controlled oligomerization of the peptoid monomers was performed manually and robotically with in situ activation by either benzotriazol-1-yloxytris(pyrrolidino)phosphonium hexafluorophosphate or bromotris(pyrrolidino)phosphonium hexaflurophosphate. Other steps were identical to peptide synthesis using alpha-(9-fluorenylmethoxycarbonyl)amino acids. A total of 15 monomers and 10 oligomers (peptoids) are described. Preliminary data are presented on the stability of a representative oligopeptoid to enzymatic hydrolysis. Peptoid versions of peptide ligands of three biological systems (bovine pancreatic alpha-amylase, hepatitis A virus 3C proteinase, and human immunodeficiency virus transactivator-responsive element RNA) were found with affinities comparable to those of the corresponding peptides. The potential use of libraries of these compounds in receptor- or enzyme-based assays is discussed. PMID:1409642

Rice choline monooxygenase (OsCMO) protein functions in enhancing glycine betaine biosynthesis in transgenic tobacco but does not accumulate in rice (Oryza sativa L. ssp. japonica).

PubMed

Luo, Di; Niu, Xiangli; Yu, Jinde; Yan, Jun; Gou, Xiaojun; Lu, Bao-Rong; Liu, Yongsheng

2012-09-01

Glycine betaine (GB) is a compatible quaternary amine that enables plants to tolerate abiotic stresses, including salt, drought and cold. In plants, GB is synthesized through two-step of successive oxidations from choline, catalyzed by choline monooxygenase (CMO) and betaine aldehyde dehydrogenase (BADH), respectively. Rice is considered as a typical non-GB accumulating species, although the entire genome sequencing revealed rice contains orthologs of both CMO and BADH. Several studies unraveled that rice has a functional BADH gene, but whether rice CMO gene (OsCMO) is functional or a pseudogene remains to be elucidated. In the present study, we report the functional characterization of rice CMO gene. The OsCMO gene was isolated from rice cv. Nipponbare (Oryza sativa L. ssp. japonica) using RT-PCR. Northern blot demonstrated the transcription of OsCMO is enhanced by salt stress. Transgenic tobacco plants overexpressing OsCMO results in increased GB content and elevated tolerance to salt stress. Immunoblotting analysis demonstrates that a functional OsCMO protein with correct size was present in transgenic tobacco but rarely accumulated in wild-type rice plants. Surprisingly, a large amount of truncated proteins derived from OsCMO was induced in the rice seedlings in response to salt stresses. This suggests that it is the lack of a functional OsCMO protein that presumably results in non-GB accumulation in the tested rice plant. Expression and transgenic studies demonstrate OsCMO is transcriptionally induced in response to salt stress and functions in increasing glycinebetaine accumulation and enhancing tolerance to salt stress. Immunoblotting analysis suggests that no accumulation of glycinebetaine in the Japonica rice plant presumably results from lack of a functional OsCMO protein.

Physical-chemical evaluation of hydraulic fracturing chemicals in the context of produced water treatment.

PubMed

Camarillo, Mary Kay; Domen, Jeremy K; Stringfellow, William T

2016-12-01

Produced water is a significant waste stream that can be treated and reused; however, the removal of production chemicals-such as those added in hydraulic fracturing-must be addressed. One motivation for treating and reusing produced water is that current disposal methods-typically consisting of deep well injection and percolation in infiltration pits-are being limited. Furthermore, oil and gas production often occurs in arid regions where there is demand for new water sources. In this paper, hydraulic fracturing chemical additive data from California are used as a case study where physical-chemical and biodegradation data are summarized and used to screen for appropriate produced water treatment technologies. The data indicate that hydraulic fracturing chemicals are largely treatable; however, data are missing for 24 of the 193 chemical additives identified. More than one-third of organic chemicals have data indicating biodegradability, suggesting biological treatment would be effective. Adsorption-based methods and partitioning of chemicals into oil for subsequent separation is expected to be effective for approximately one-third of chemicals. Volatilization-based treatment methods (e.g. air stripping) will only be effective for approximately 10% of chemicals. Reverse osmosis is a good catch-all with over 70% of organic chemicals expected to be removed efficiently. Other technologies such as electrocoagulation and advanced oxidation are promising but lack demonstration. Chemicals of most concern due to prevalence, toxicity, and lack of data include propargyl alcohol, 2-mercaptoethyl alcohol, tetrakis hydroxymethyl-phosphonium sulfate, thioglycolic acid, 2-bromo-3-nitrilopropionamide, formaldehyde polymers, polymers of acrylic acid, quaternary ammonium compounds, and surfactants (e.g. ethoxylated alcohols). Future studies should examine the fate of hydraulic fracturing chemicals in produced water treatment trains to demonstrate removal and clarify interactions between upstream and downstream processes. Copyright © 2016 Elsevier Ltd. All rights reserved.

Cationic boranes for the complexation of fluoride ions in water below the 4 ppm maximum contaminant level.

PubMed

Kim, Youngmin; Gabbaï, François P

2009-03-11

In search of a molecular receptor that could bind fluoride ions in water below the maximum contaminant level of 4 ppm set by the Environmental Protection Agency (EPA), we have investigated the water stability and fluoride binding properties of a series of phosphonium boranes of general formula [p-(Mes(2)B)C(6)H(4)(PPh(2)R)](+) with R = Me ([1](+)), Et ([2](+)), n-Pr ([3](+)), and Ph ([4](+)). These phosphonium boranes are water stable and react reversibly with water to form the corresponding zwitterionic hydroxide complexes of general formula p-(Mes(2)(HO)B)C(6)H(4)(PPh(2)R). They also react with fluoride ions to form the corresponding zwitterionic fluoride complexes of general formula p-(Mes(2)(F)B)C(6)H(4)(PPh(2)R). Spectrophotometric acid-base titrations carried out in H(2)O/MeOH (9:1 vol.) afford pK(R+) values of 7.3(+/-0.07) for [1](+), 6.92(+/-0.1) for [2](+), 6.59(+/-0.08) for [3](+), and 6.08(+/-0.09) for [4](+), thereby indicating that the Lewis acidity of the cationic boranes increases in following order: [1](+) < [2](+) < [3](+) < [4](+). In agreement with this observation, fluoride titration experiments in H(2)O/MeOH (9:1 vol.) show that the fluoride binding constants (K = 840(+/-50) M(-1) for [1](+), 2500(+/-200) M(-1) for [2](+), 4000(+/-300) M(-1) for [3](+), and 10 500(+/-1000) M(-1) for [4](+)) increase in the same order. These results show that the Lewis acidity of the cationic boranes increases with their hydrophobicity. The resulting Lewis acidity increase is substantial and exceeds 1 order of magnitude on going from [1](+) to [4](+). In turn, [4](+) is sufficiently fluorophilic to bind fluoride ions below the EPA contaminant level in pure water. These results indicate that phosphonium boranes related to [4](+) could be used as molecular recognition units in chemosensors for drinking water analysis.

Toxicity evaluation of selected ammonium-based ionic liquid forms with MCPP and dicamba moieties on Pseudomonas putida.

PubMed

Piotrowska, Aleksandra; Syguda, Anna; Wyrwas, Bogdan; Chrzanowski, Łukasz; Heipieper, Hermann J

2017-01-01

Combination of the hydrophilic herbicidal anion with hydrophobic, antimicrobial ammonium cation allows to obtain compounds in ionic liquid form with better properties then conventional herbicides. Both cation and anion can be modified by selection of herbicide and the length of alkyl chains in cation structure. However the knowledge of their potential toxic effects are still limited. Furthermore, the relation between hydrophobicity associated with the length of alkyl chains and toxicity for ionic liquids has not been thoroughly studied. Therefore we investigated toxic effects of herbicidal ionic liquid forms on growth inhibition, given as EC 50, of the common soil bacterium Pseudomonas putida. We thereby concentrated on quaternary ammonium salts. Analyzed compounds were composed of dicamba or MCPP moieties and cation with various alkyl chain lengths (n = 6,8,10) We compared them with commercial herbicides, and ammonium-based ionic liquids with neutral anion (Br - ). In addition, cis-trans isomerisation of unsaturated membrane fatty acids in Pseudomonas putida was applied as the proxy for toxicity and membrane activity. We showed that toxicity increased with the length of alkyl chains. However, this correlation is only valid for six and eight carbon atom in alkyl chains, where for n = 10 the EC 50 values rise by one order of magnitude. In our studies, the herbicidal ionic liquids [C 10 ,C 10 ,C 1 ,C 1 N][MCPP] and [C 10 ,C 10 ,C 1 ,C 1 N][dicamba] showed the lowest toxicity among analyzed quaternary ammonium salts and comparable toxicity with corresponding herbicides. No clear increase in toxicity could be followed by changing the anion moieties for ammonium-based ionic liquid forms. Copyright © 2016 Elsevier Ltd. All rights reserved.

A History of Repeated Failures: Stratigraphy of the Currituck and Cape Fear Slide Complexes on the Central U.S. Atlantic Margin

NASA Astrophysics Data System (ADS)

Hill, J. C.; Brothers, D. S.; Ten Brink, U. S.

2016-12-01

The Currituck and Cape Fear Slide complexes, offshore of North Carolina, are two of the largest (>150 km3) submarine slope failure provinces on the U.S. Atlantic margin. Detailed stratigraphy of these slides and the surrounding regions is derived from a combination of high-resolution sparker multichannel seismic (MCS) data collected by the USGS in 2012, airgun MCS collected as part of the NSF GeoPRISMs Community Seismic Experiment in 2014 & legacy industry airgun MCS data collected in 1970s and 80s. Both the Currituck and Cape Fear Slide complexes are located in regions with high sediment input that resulted in the development of a broad, low gradient (<6°) margin with thick slope sediment accumulation since at least the Miocene. Bedding parallel failure planes highlight the influence of subsurface stratigraphy here. Differential compaction across buried scarps and other erosional surfaces found in proximity to many of the headwalls may have contributed to excess pore pressure in these zones, setting the stage for repeated failures. Within the Currituck Slide complex, there appear to be several buried mass transport deposits (MTDs) within both the Quaternary and Pliocene sections that may be related to buried scarps found beneath both the upper and lower headwalls. At the Cape Fear Slide, the Quaternary section upslope of a large salt diapir displays evidence of possible downslope creep folding within strata that downlap onto a possible buried failure plane. While submarine slope failure along this portion of the margin has long been linked with hydrate dissociation and/or salt tectonics, features that are pervasive along the margin, our new stratigraphic analyses suggest that antecedent margin physiography and sediment loading may be critical factors in determining the locations of large-scale slope failures.

21 CFR 176.300 - Slimicides.

Code of Federal Regulations, 2013 CFR

2013-04-01

...) cyclohexanone 1,2-Bis(monobromoacetoxy) ethane [CA Reg. No. 3785-34-0] At a maximum level of 0.10 pound per ton... Methylenebisbutanethiolsulfonate Methylenebisthiocyanate 2-Nitrobutyl bromoacetate [CA Reg. No. 32815-96-6] At a maximum level of 0...)phosphonium sulfate (CAS Reg. No. 55566-30-8) Maximum use level of 84 mg/kg in the pulp slurry. The additive...

21 CFR 176.300 - Slimicides.

Code of Federal Regulations, 2012 CFR

2012-04-01

...) cyclohexanone 1,2-Bis(monobromoacetoxy) ethane [CA Reg. No. 3785-34-0] At a maximum level of 0.10 pound per ton... Methylenebisbutanethiolsulfonate Methylenebisthiocyanate 2-Nitrobutyl bromoacetate [CA Reg. No. 32815-96-6] At a maximum level of 0...)phosphonium sulfate (CAS Reg. No. 55566-30-8) Maximum use level of 84 mg/kg in the pulp slurry. The additive...

Aqueous biphasic systems formed by deep eutectic solvent and new-type salts for the high-performance extraction of pigments.

PubMed

Zhang, Hongmei; Wang, Yuzhi; Zhou, Yigang; Chen, Jing; Wei, Xiaoxiao; Xu, Panli

2018-05-01

Deep eutectic solvent (DES) composed of polypropylene glycol 400 (PPG 400) and tetrabutylammonium bromide (TBAB) was combined with a series of new-type salts such as quaternary ammonium salts, amino acid and polyols to form Aqueous Biphasic Systems (ABSs). Phase-forming ability of the salts was investigated firstly. The results showed that polyols had a relatively weak power to produce phases within studied scopes. And the shorter of carbon chain length of salts, the easier to obtain phase-splitting. Then partitioning of three pigments in PPG 400/betaine-based ABSs was addressed to investigate the effect of pigments' hydrophobicity on extraction efficiency. It was found that an increase in hydrophobicity contributed to the migration of pigments in the DES-rich phase. On the other hand, with a decline in phase-forming ability of salts, the extraction efficiency of the whole systems started to go down gradually. Based on the results, selective separation experiment was conducted successfully in the PPG 400/betaine-based systems, including more than 93.00% Sudan Ⅲ in the top phase and about 80.00% sunset yellow FCF/amaranth in the bottom phase. Additionally, ABSs constructed by DES/betaine for partitioning amaranth were further utilized to explore the performances of influence factors and back extraction. It can be concluded that after the optimization above 98.00% amaranth was transferred into the top phase. And 67.98% amaranth can be transferred into the bottom phase in back-extraction experiment. At last, dynamic light scattering (DLS) and transmission electron microscope (TEM) were applied to probe into extraction mechanism. The results demonstrated that hydrophobicity played an important role in the separation process of pigments. Through combining with new-type DES, this work was devoted to introducing plentiful salts as novel compositions of ABSs and providing an eco-friendly extraction way for partitioning pigments, which boosted development of ABSs in the monitoring food safety field. Copyright © 2018 Elsevier B.V. All rights reserved.

Ylide Ligands as Building Blocks for Bioactive Group 11 Metal Complexes.

PubMed

Gimeno, M Concepción; Johnson, Alice; Marzo, Isabel

2018-05-22

The reactivity of the phosphonium salt, (cyanomethyl)triphenylphosphonium chloride, and the ylide, triphenylphosphoniumcyanomethylide, towards group eleven metal complexes is described. Mononuclear neutral gold(I) and gold(III) complexes of the type [AuX{CH(CN)PPh3}] or [AuX3{CH(CN)PPh3}], and cationic derivatives such as [AuL{CH(CN)PPh3}]X have been prepared. Surprisingly the cationic gold species could only be prepared with ligands with a large steric hindrance such as bulky NHCs or the JohnPhos phosphine, in contrast with silver and copper derivatives which have dimeric structures with coordination to the cyano group of the ylide. Bis(ylide)metal complexes have been synthesised in which a different structure is observed for gold compared to copper and silver. While gold shows mononuclear species, the silver complex presents a bidimensional polymeric structure as a result of further coordination of the silver centre to the nitrogen of the cyano group. These complexes possess two chiral centres and the gold compound is obtained as a mixture of diastereoisomers, whereas the copper and silver derivatives afford only one diastereroisomer. These compounds were screened for the in vitro cytotoxic activity against the human lung carcinoma cell line (A549). The IC50 values reveal an excellent cytotoxic activity for these metal complexes compared with cisplatin. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Exploring the Use of Ionic Liquid Mixtures to Enhance the Performance of Dicationic Ionic Liquids

DOE PAGES

Lall-Ramnarine, Sharon I.; Suarez, Sophia N.; Fernandez, Eddie D.; ...

2017-05-06

Dicationic ionic liquids (DILs) of diverse structural architectures (including symmetrical and asymmetrical ammonium, phosphonium and heterodications and the bis(trifluoromethylsulfonyl)amide (NTf 2 -) anion) have been prepared and used as additives to N-methyl-N-ethoxyethylpyrrolidinium (P 1EOE) NTf 2, a relatively high-performing IL in terms of its transport properties (viscosity 53 mPa s). The three-ion, binary IL mixtures were characterized for their thermal and transport properties using differential scanning calorimetry, temperature dependent viscosity, conductivity and Pulsed Gradient Spin Echo (PGSE) NMR. Variable temperature 1H, 19F and 31P self-diffusion coefficients were determined at 25, 60 and 75°C. The order of the diffusion coefficients wasmore » D(P 1EOE +) > D(anion) > D(dication), and the composition of the dication had a strong effect on the degree to which diffusion of all three species is more or less coupled. IL mixtures containing about 30 mol % of the dicationic NTf 2 and 70 mol % of P 1EOE NTf 2 resulted in a significant decrease in glass transition temperatures and viscosities compared to the pure DIL. The mixtures extended the liquid range and potential for practical applications significantly. Finally, the data obtained here provides insight into the future design of dicationic salts tailored to exhibit lower viscosity and higher conductivities.« less

Improvement of Mechanical Properties in Natural Rubber with Organic Fillers

NASA Astrophysics Data System (ADS)

Gonzales-Fernandes, M.; Bastos, Andrade C. G.; Esper, F. J.; Valenzuela-Diaz, F. R.; Wiebeck, H.

When added to polymeric matrices, organophilic clay transforms the performance of the resulting composites. A natural rubber matrix with different loads was prepared as bentonite chocolate B modified by sodification and treated with ammonium quaternary salt with cellulose charge, cardboard and palm fiber. After the mixture of natural rubber in a roller mill with the additives and subsequent addition of loads individually, plates were vulcanized for fabricating specimens. We measured the mechanical properties of traction and the interlayer distances analyzed by XRD. The aim of the paper is to show that the composite obtained improved in mechanical properties as compared to plates without the addition of loads.

A novel microreactor approach for analysis of ketones and aldehydes in breath.

PubMed

Fu, Xiao-An; Li, Mingxiao; Biswas, Souvik; Nantz, Michael H; Higashi, Richard M

2011-11-21

We report a fabricated microreactor with thousands of micropillars in channels. Each micropillar surface is chemically functionalized to selectively preconcentrate gaseous ketones and aldehydes of exhaled breath and to enhance ultra-trace, rapid analysis by direct-infusion Fourier transform-ion cyclotron resonance (FT-ICR) mass spectrometry (MS). The micropillar reactive coating contains the quaternary ammonium aminooxy salt 2-(aminooxy)ethyl-N,N,N-trimethylammonium iodide (ATM) for capturing trace carbonyl VOCs by means of an oximation reaction. We demonstrate the utility of this approach for detection of C(1) to C(12) aldehydes and ketones in exhaled breath, but the approach is applicable to any gaseous sample.

Mercury(II) complexes of unsymmetric phosphorus ylides: Synthesis, spectroscopic and antibacterial activity studies

NASA Astrophysics Data System (ADS)

Sabounchei, Seyyed Javad; Panahimehr, Mohammad; Hosseinzadeh, Marjan; Karamian, Roya; Asadbegy, Mostafa; Masumi, Azadeh

2014-03-01

The reaction of Ph2PCH2PPh2 (dppm) with 2-bromo-3-nitroacetophenone and 2,2‧,4‧-trichloroacetophenone in chloroform produce the new phosphonium salts [Ph2PCH2PPh2CH2C(O)C6H4NO2]Br (1) and [Ph2PCH2PPh2CH2C(O)C6H3Cl2]Cl (2). Further, by reaction of the monophosphonium salts of dppm with the strong base triethylaminethe corresponding bidentate phosphorus ylides, Ph2PCH2PPh2C(H)C(O)C6H4NO2 (3) and Ph2PCH2PPh2C(H)C(O)C6H3Cl2 (4) were obtained. The reaction of these ligands with mercury(II) halides in dry methanol led to the formation of the mononuclear complexes {HgX2[(Ph2PCH2PPh2C(H)C(O)C6H4NO2)]} [X = Cl (5), Br (6), I (7)] and {HgX2[(Ph2PCH2PPh2C(H)C(O)C6H3Cl2)]} [X = Cl (8), Br (9), I (10)]. Characterization of the obtained compounds was performed by elemental analysis, IR, 1H, 31P and 13C NMR. The structure of compound 1 being unequivocally determined by single crystal X-ray diffraction techniques. The mass spectrum of compound 6 (as an instance) also demonstrates the synthesize of these compounds. In all complexes the title ylides are coordinated through the ylidic carbon and the phosphine atom. These compounds form five membered ring under complexation. The antibacterial effects of DMSO solutions of the ligands and their metal complexes were evaluated by the disc diffusion method against six Gram positive and negative bacteria. All compounds represent antibacterial activity against these bacteria with high levels of inhibitory potency exhibited against the Gram positive species.

Investigations of the ex situ ionic conductivities at 30 degrees C of metal-cation-free quaternary ammonium alkaline anion-exchange membranes in static atmospheres of different relative humidities.

PubMed

Varcoe, John R

2007-03-28

This article presents the first systematic study of the effect of Relative Humidity (RH) on the water content and hydroxide ion conductivity of quaternary ammonium-based Alkaline Anion-Exchange Membranes (AAEMs). These AAEMs have been developed specifically for application in alkaline membrane fuel cells, where conductivities of >0.01 S cm(-1) are mandatory. When fully hydrated, an ETFE-based radiation-grafted AAEM exhibited a hydroxide ion conductivity of 0.030 +/- 0.005 S cm(-1) at 30 degrees C without additional incorporation of metal hydroxide salts; this is contrary to the previous wisdom that anion-exchange membranes are very low in ionic conductivity and represents a significant breakthrough for metal-cation-free alkaline ionomers. Desirably, this AAEM also showed increased dimensional stability on full hydration compared to a Nafion-115 proton-exchange membrane; this dimensional stability is further improved (with no concomitant reduction in ionic conductivity) with a commercial AAEM of similar density but containing additional cross-linking. However, all of the AAEMs evaluated in this study demonstrated unacceptably low conductivities when the humidity of the surrounding static atmospheres was reduced (RH = 33-91%); this highlights the requirement for continued AAEM development for operation in H(2)/air fuel cells with low humidity gas supplies. Preliminary investigations indicate that the activation energies for OH(-) conduction in these quaternary ammonium-based solid polymer electrolytes are typically 2-3 times higher than for H(+) conduction in acidic Nafion-115 at all humidities.

Luminophores of tunable colors from ternary Ag-In-S and quaternary Ag-In-Zn-S nanocrystals covering the visible to near-infrared spectral range.

PubMed

Gabka, Grzegorz; Bujak, Piotr; Kotwica, Kamil; Ostrowski, Andrzej; Lisowski, Wojciech; Sobczak, Janusz W; Pron, Adam

2017-01-04

Ternary Ag-In-S or quaternary Ag-In-Zn-S nanocrystals were prepared from simple precursors (silver nitrate, indium(iii) chloride, zinc stearate in a mixture of DDT and ODE) by injecting a solution of elemental sulfur into OLA. Ternary nanocrystals were modified by depositing either a ZnS or a CdS shell, yielding type I and type II core/shell systems exhibiting photoluminescence QY in the range of 12-16%. Careful optimization of the reaction conditions allowed alloyed quaternary Ag-In-Zn-S nanocrystals exhibiting tunable photoluminescence in the spectral range of 520-720 nm with a QY of 48% and 59% for green and red radiations, respectively, to be obtained. 1 H NMR analysis of the nanocrystal organic shell, after dissolution of its inorganic core, indicated that surfacial sulfur atoms were covalently bonded to aliphatic chains whereas surfacial cations were coordinated by amines and carboxylate anions. No thiol-type ligands were detected. Transfer of the prepared nanocrystals to water could be achieved in one step by exchanging the initial ligands for 11-mercaptoundecanoic ones resulting in a QY value of 31%. A new Ag-In-Zn-S nanocrystal preparation method was elaborated in which indium and zinc salts of fatty acids were used as cation precursors and DDT was replaced by thioacetamide. This original DDT-free method enabled similar tuning of the photoluminescence properties of the nanocrystals as in the previous method; however the measured photoluminescence QYs were three times lower. Hence, further optimization of the new method is required.

Bifunctional Asymmetric Catalysis with Hydrogen Chloride: Enantioselective Ring-Opening of Aziridines Catalyzed by a Phosphinothiourea

PubMed Central

Mita, Tsuyoshi; Jacobsen, Eric N.

2009-01-01

Ring-opening of aziridines with hydrogen chloride to form β-chloroamine derivatives is catalyzed by a chiral phosphinothiourea derivative in high yields and with high enantioselectivities. On the basis of 31P NMR studies, activation of HCl appears to proceed via quantitative protonation of the catalyst to afford a phosphonium chloride complex. PMID:20161432

Mechanism of the sulfurisation of phosphines and phosphites using 3-amino-1,2,4-dithiazole-5-thione (xanthane hydride).

PubMed

Hanusek, Jirí; Russell, Mark A; Laws, Andrew P; Jansa, Petr; Atherton, John H; Fettes, Kevin; Page, Michael I

2007-02-07

Contrary to a previous report, the sulfurisation of phosphorus(III) derivatives by 3-amino-1,2,4-dithiazole-5-thione (xanthane hydride) does not yield carbon disulfide and cyanamide as the additional reaction products. The reaction of xanthane hydride with triphenyl phosphine or trimethyl phosphite yields triphenyl phosphine sulfide or trimethyl thiophosphate, respectively, and thiocarbamoyl isothiocyanate which has been trapped with nucleophiles. The reaction pathway involves initial nucleophilic attack of the phosphorus at sulfur next to the thiocarbonyl group of xanthane hydride followed by decomposition of the phosphonium intermediate formed to products. The Hammett rho-values for the sulfurisation of substituted triphenyl phosphines and triphenyl phosphites in acetonitrile are approximately -1.0. The entropies of activation are very negative (-114+/-15 J mol-1 K-1) with little dependence on solvent which is consistent with a bimolecular association step leading to the transition state. The negative values of DeltaS(not equal) and rho values indicate that the rate limiting step of the sulfurisation reaction is formation of the phosphonium ion intermediate which has an early transition state with little covalent bond formation. The site of nucleophilic attack has been also confirmed using computational calculations.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barnhill, William C.; Qu, Jun; Luo, Huimin

In our previous work we suggest great potential for a phosphonium-organophosphate ionic liquid (IL) as an antiwear lubricant additive. In this study, a set of five ILs were carefully designed and synthesized, with identical organophosphate anions but dissimilar phosphonium cations, to allow systematic investigation of the effects of cation alkyl chain length and symmetry on physicochemical and tribological properties. Symmetric cations with shorter alkyl chains seem to increase the density and thermal stability due to closer packing. On the other hand, either higher cation symmetry or longer alkyl moieties induce a higher viscosity, though the viscosity index is dependent moremore » on molecular mass than on symmetry. While a larger cation size generally increases an IL’s solubility in nonpolar hydrocarbon oils, six-carbon seems to be the critical minimum alkyl chain length for high oil miscibility. Both the two ILs, that are mutually oil miscible, have demonstrated promising lubricating performance at 1.04% treat rate, though the symmetric-cation IL moderately outperformed the asymmetric-cation IL. Moreover, characterizations on the tribofilm formed by the best-performing symmetric-cation IL revealed the film thickness, nanostructure, and chemical composition. Our results provide fundamental insights for future molecular design in developing oil-soluble ILs as lubricant additives.« less

Synthesis of substituted 1,3-diesters of glycerol using wittig chemistry.

PubMed

Lowe, Henry I C; Toyang, Ngeh J; Watson, Charah T; Bryant, Joseph

2014-05-01

1,3-di-O-Cinnamoyl-glycerol is a natural compound isolated from a Jamaican medicinal plant commonly referred to as Ball moss (Tillandsia recurvata). The synthesis of this compound was achieved via a Wittig chemistry process. The synthetic approach started with acylation of a di-protected glycerol with cinnamoyl chloride, deprotection of the glycerol moiety, reaction of the primary alcohol with bromo acetylbromide followed by treatment with triphenyl phosphine to give the corresponding phosphonium bromide. The phosphonium bromide was then converted in situ to the Wittig reagent which is the basis for a novel route to 1,3-di-O-cinnamoyl glycerol. Four analogs were also synthesized, three of which are new and are being reported in this article for the first time. The new compounds include 3-(3,4-diemthoxy-phenyl)-acrylic acid 2-hydroxy-3-(3-ptolyl-acryloyloxy)-propyl ester (3), 2-acetoxy-5-((E)-3-(3-((E)-3-(3,4-dimethoxyphenyl)acryloyloxy)-2-hydropropoxy)-3-oxoprop- 1-enyl)benzoic acid (4) and 4-((E)-3-(3-((E)-3-(3,4-dimethoxyphenyl)acryloyloxy)-2-hydropropoxy)-3-oxoprop-1-enyl)benzoic acid (5). The compounds showed no activity in our anticancer assay.

Analytical Method for the Detection of Residual Active Ingredients Found in Neutralized Suspensions of Antimicrobial Products.

PubMed

Kamel, Alaa; Tomasino, Stephen F

2017-03-01

An analytical method for determining the presence and levels of residual active ingredients found in neutralized suspensions of phenolic and quaternary ammonium salt-based antimicrobial products was developed using solid-phase extraction in combination with LC-tandem MS. A single-laboratory validation of the method was performed at three concentration levels for the quaternary ammonium compounds (also referred to as benzalkonium chlorides or BACs) and the phenols in the presence of letheen broth neutralizer at 2.5 and 2.75 μg/mL, respectively, as well as at dilutions of 1:10 and 1:100 in those concentrations. The method's lowest LODs were 0.005 μg/g for BACs and 0.006 μg/g for phenols. The average recovery of the fortified samples for both active ingredients ranged between 80 and 124%, and RSDs were generally <20%. In a related study, the effectiveness of letheen broth with and without sodium thiosulfate was evaluated as a neutralizer for sodium hypochlorite. The results showed that letheen broth without sodium thiosulfate neutralizes chlorine concentrations up to 60 ppm, and that 200 μg sodium thiosulfate are required to neutralize a 72 ppm concentrated chlorine solution in letheen broth.

Exploration of a Metastable Normal Spinel Phase Diagram for the Quaternary Li–Ni–Mn–Co–O System

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kan, Wang Hay; Huq, Ashfia; Manthiram, Arumugam

2016-02-27

In an attempt to enlarge the normal spinel phase diagram for the quaternary Li-Ni-Mn-Co-O system, the transformation at moderate temperatures (150-210 °C) of layered Li 0.5(Ni 1-y-zMn yCo z)O 2 (Rmore » $$\\bar{3}$$m), which were obtained by an ambient-temperature extraction of lithium from Li 0.5(Ni 1-y-zMn yCo z)O 2, into normal spinel-like (Fd$$\\bar{3}$$m) Li(Ni 1-y-zMn yCo z) 2O 4 has been investigated. The phase-conversion mechanism has been studied by joint time-of-flight (TOF) neutron and X-ray diffractions, thermogravimetric analysis, and bond valence sum map. The ionic diffusion of lithium (3a, 6c) and nickel (3a, 3b) ions has been quantified as a function of temperature. The investigated spinel phases are metastable, and they are subject to change into rock-salt phases at higher temperatures. The phases have been characterized as cathodes in lithium-ion cells. Finally, the study may serve as a strategic model to access other metastable phases by low-temperature synthesis approaches.« less

Influence of the anion nature and alkyl substituents in the behavior of ionic liquids derived from phenylpyridines

NASA Astrophysics Data System (ADS)

Dreyse, Paulina; Alarcón, Antonia; Galdámez, Antonio; González, Iván; Cortés-Arriagada, Diego; Castillo, Francisco; Mella, Andy

2018-02-01

Quaternary alkyl 2-phenylpyridinium and 2-(2,4-difluorophenyl)pyridinium amines with iodide, hexafluorophosphate and bis(trifluoromethylsulfonyl)imide anions have been fully characterized by 1H NMR, FT-IR and MALDI mass spectroscopic methods and studied by quantum chemistry calculations. The compounds with bis(trifluoromethylsulfonyl)imide anion can be classified as ionic liquids, because they melt at room temperature. The quaternary amines with iodide and hexafluorophosphate anions are solid at 25 °C. The X-ray diffraction characterization of the 2-(2,4-difluorophenyl)-1-methylphenylpyridinium hexafluorophosphate and 1-ethyl-2-(2,4-difluorophenyl)phenylpyridinium hexafluorophosphate show an extensive series of Csbnd H⋯F, Csbnd F⋯π and Psbnd F⋯π intermolecular interactions, which give rise to a supramolecular network. The relationship between the solid-state structures and the melting points is discussed by the evaluation of the thermal behavior based on experimental data from Differential Scanning Calorimetry (DSC) studies, and also using the analysis of the ion pairs binding energies. These new compounds based on phenylpyridine allow us to grow the diversity of ionic liquids and their crystalline salts, increasing the knowledge about the chemical and physical properties of these ionic species.

Studies of quaternary saline lakes-II. Isotopic and compositional changes during desiccation of the brines in Owens Lake, California, 1969-1971

USGS Publications Warehouse

Friedman, I.; Smith, G.I.; Hardcastle, Kenneth G.

1976-01-01

Owens Lake is an alkaline salt lake in a closed basin in southeast California. It is normally nearly dry, but in early 1969, an abnormal runoff from the Sierra Nevada flooded it to a maximum depth of 2??4 m. By late summer of 1971, the lake was again nearly dry and the dissolved salts recrystallized. Changes in the chemistry, pH, and deuterium content were monitored during desiccation. During flooding, salts (mostly trona, halite, and burkeite) dissolved slowly from the lake floor. Their concentration in the lake waters increased as evaporation removed water and salts again crystallized, but winter temperatures caused precipitation of some salts and the following summer warming caused their solution, resulting in seasonal variations in the concentration patterns of some ions. The pH values (9??4-10??4) changed with time but showed no detectable diurnal pattern. The deuterium concentration increased during evaporation and appeared to be in equilibrium with vapor leaving the lake according to the Rayleigh equation. The effective ??(D/H in liquid/D/H in vapor) decreased as salinity increased; the earliest measured value was 1??069 [as total dissolved solids (TDS) of lake waters changed from 136,200 to 250,400 mg/1]and the last value (calc.) was 1??025 (as TDS changed from 450,000 to 470,300 mg/1). Deuterium exchange with the atmosphere was apparently small except during late desiccation stages when the isotopic contrast became great. Eventually, atmospheric exchange, combined with decreasing ?? and lake size and increasing salinity, stopped further deuterium concentration in the lake. The maximum contrast between atmospheric vapor and lake deuterium contents was about 110%. ?? 1976.

Seismic evidence for Messinian salt deformation and fluid circulation on the South Balearic margin (Western Mediterranean)

NASA Astrophysics Data System (ADS)

Wardell, Nigel; Camerlenghi, Angelo; Urgeles, Roger; Geletti, Riccardo; Tinivella, Umberta; Giustiniani, Michela; Accettella, Daniela

2014-05-01

The south Balearic margin is characterized by an abrupt tectonically-controlled transition between a steep continental slope (Emile Baudot escarpment) and the Algero-Balearic abyssal plain, in which Messinain salt-induced deformation affects the seafloor morphology. Multichannel seismic profiles, multibeam bathymetry, and shallow seismic data demonstrate that the extent of salt deformation does not coincide with the bathymetric plain-slope transition. Instead, deformation occurs south of linear structure in the abyssal plain located some tens of kilometres from the base of the slope. The quality of the multi-channel seismic record in the deep water deformed area is severely decreased by the three dimensional character of the salt structures. However, the abyssal plain near the base of the slope reveals details on the Messinian sequence, its structure, post-Messinan deformation, and relation with subsurface fluids. The analysis of part of the EUROFLEETS SALTFLU multichannel seismic data set has included detailed RMS velocity analysis, post-stack and pre-stack time migration. An anomalously thick (up to 800 ms twt) acoustically laminated unit comprising the Messinian Upper Unit (UU) is present near the base of the slope and is characterized by syn-sedimentary gentle symmetric folding. The crests of such folds are affected by small-offset, layer-bound fractures and faults propagating from the upper part to the UU to the Plio-Quaternary sequence. Amplitude anomalies, polarity inversion and at times acoustic blanking reveal the presence of fluids (presumably gas) within the Messinian sequence. A clear seismic evidence for the Mobile Unit (MU, or salt layer) is missing in this area. Seismic evidence for the MU exists south of the linear structural boundary, where salt induced deformation has created vertical displacements of several hundreds of metres, diapiric growth, and at least two salt/mud piercement structures at the seafloor. In the highly deformed area, the UU and the Lower Unit (LU) appear to amalgamate as a consequence of complete salt withdrawal around diapirs. The seismic analysis is focussed on determining whether the boundary between low and high degree of deformation in the abyssal plain is determined by the limit of the salt distribution. In this case the northern limit of the Messinian pure salt basin would not coincide with the present day continental slope, thus requiring either a strong control of Messinian tectonic structures an salt deposition and/or a contamination of salt with clastics.

Studies of Quaternary saline lakes-III. Mineral, chemical, and isotopic evidence of salt solution and crystallization processes in Owens Lake, California, 1969-1971

USGS Publications Warehouse

Smith, G.I.; Friedman, I.; McLaughlin, R.J.

1987-01-01

As a consequence of the 1969-1970 flooding of normally dry Owens Lake, a 2.4-m-deep lake formed and 20% of the 2-m-thick salt bed dissolved in it. Its desiccation began August 1969, and salts started crystallizing September 1970, ending August 1971. Mineralogic, brine-composition, and stable-isotope data plus field observations showed that while the evolving brine composition established the general crystallization timetable and range of primary and secondary mineral assemblages, it was the daily, monthly, and seasonal temperature changes that controlled the details of timing and mineralogy during this depositional process. Deuterium analyses of lake brine, interstitial brine, and hydrated saline phases helped confirm the sequence of mineral crystallizations and transformations, and they documented the sources and temperatures of waters involved in the reactions. Salts first crystallized as floating rafts on the lake surface. Natron and mirabilite, salts whose solubilities decrease greatly with lowering temperatures, crystallized late at night in winter, when surface-water temperatures reached their minima; trona, nahcolite, burkeite, and halite, salts with solubilities less sensitive to temperature, crystallized during the afternoon in summer, when surface salinities reached their maxima. However, different temperatures were generally associated with crystallization (at the surface) and accumulation (on the lake floor) because short-term temperature changes were transmitted to surface and bottom waters at different rates. Consequently, even when solubilities were exceeded at the surface, salts were preserved or not as a function of bottom-water temperatures. Halite, a nearly temperature-insensitive salt, was always preserved. Monitoring the lake-brine chemistry and mineralogy of the accumulating salts shows: (1) An estimated 0.9 ?? 106 tons of CO2 was released to the atmosphere or consumed by the lake's biomass prior to most salt crystallization. (2) After deposition, some salts reacted in situ to form other minerals in less than one month, and all salts (except halite) decomposed or recrystallized at least once in response to seasons. (3) Warming in early 1971 caused solution of all the mirabilite and some of the natron deposited a few months earlier, a deepening of the lake (though the lake-surface lowered), and an increase in dissolved solids. (4) Phase and solubility-index data suggest that at the close of desiccation, Na2CO3??7H2O, never reported as a mineral, could have been the next phase to crystallize. ?? 1987.

Studies of geology and hydrology in the Basin and Range Province, Southwestern United States, for isolation of high-level radioactive waste - Characterization of the Bonneville region, Utah and Nevada

USGS Publications Warehouse

Bedinger, M.S.; Sargent, K.A.; Langer, William H.

1990-01-01

The Bonneville region of the Basin and Range province in westcentral Utah and adjacent Nevada includes several basins lying south of the Great Salt Lake Desert. Physiographically, the region consists of linear, north-trending mountain ranges separated by valleys, many of which are closed basins underlain by thick sequences of fill. Surface drainage of open basins and ground-water flow is to the Great Salt Lake Desert. In structure and composition the ranges are faulted Paleozoic rocks, locally intruded by Mesozoic and Tertiary plugs and stocks. In the southern and northeastern parts of the region, volcanic rocks are widespread and form large parts of some mountain ranges. The Paleozoic sedimentary rocks include great thicknesses of carbonate rocks which compose a significant aquifer in the regionMedia considered to have potential for isolation of high-level radioactive waste in the region include intrusive rocks, such as granite; ash-flow tuff; and basalt and basaltic andesite lava flows. These rock types, basin fill, and possibly other rock types, may have potential as host media in the unsaturated zone. Quaternary tectonism in the region is evidenced by seismic activity, local areas of above-normal geothermal heat flow, Quaternary faulting, late Cenozoic volcanic activity, and active vertical crustal movement. The Bonneville region is part of a large ground-water flow system that is integrated partly through basin-fill deposits, but largely through an underlying carbonate-rock sequence. The region includes: (1) several topographically closed basins with virtually no local surface discharge that are drained by the underlying carbonate-rock aquifer; (2) closed basins with local surface discharge by evapotranspiration; and (3) basins open to the Great Salt Lake Desert that discharge by groundwater underflow and evapotranspiration. The carbonate-rock aquifer discharges to large springs in the Desert and in basins tributary to the Desert. The climate is arid to semiarid with the greatest precipitation in the mountain ranges. Most recharge probably occurs by infiltration of runoff as it leaves the mountains, although some recharge probably occurs directly to the carbonate rocks in the mountain areas. The concentration of dissolved solids in ground water is generally less than 500 milligrams per liter. Dissolved-solids concentrations increase in the Great Salt Lake Desert and in major valleys adjoining the Desert. The predominant chemical constituents in ground water are calcium, magnesium, and sodium bicarbonate. Chloride-type water is associated with the higher dissolved-solids content of water in and near the Great Salt Lake Desert. The majority of the mineral occurrences containing base- and precious-metal deposits in the Bonneville region are of Tertiary age. Fluorspar is the primary industrial mineral. Coal, oil, and gas have not been produced in significant amounts.

3-Ethyl-2-methyl-5-methyl­ene-6,7-di­hydroindol-4(5H)-one

PubMed Central

Sonar, Vijayakumar N.; Parkin, Sean; Crooks, Peter A.

2008-01-01

The title compound, C12H15NO, a degradation product of molindone hydro­chloride, was prepared by the reaction of molindone with methyl iodide and subsequent reaction of the resulting quaternary ammonium salt with 2N aqueous sodium hydroxide. The newly formed double bond is exocyclic in nature and the carbonyl group is conjugated with the π-electrons of the pyrrole ring. The six-membered ring is in the half-chair conformation. The H atom attached to the N atom is involved in an inter­molecular hydrogen bond with the O atom of a screw-related mol­ecule, thus forming a continuous chain. PMID:21200723

Amination of electrophilic aromatic compounds by vicarious nucleophilic substitution

DOEpatents

Mitchell, Alexander R.; Pagoria, Philip F.; Schmidt, Robert D.

2000-01-01

The present invention relates to a process to aminate electrophilic aromatic compounds by vicarious nucleophilic substitution of hydrogen using quaternary hydrazinium salts. The use of trialkylhydrazinium halide, e.g., trimethylhydrazinium iodide, as well as hydroxylamine, alkoxylamines, and 4-amino-1,2,4-triazole to produce aminated aromatic structures, such as 1,3-diamino-2,4,6-trinitrobenzene (DATB), 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) and 3,5-diamino-2,4,6-trinitrotoluene (DATNT), is described. DATB and TATB are useful insensitive high explosives. TATB is also used for the preparation of benzenehexamine, a starting material for the synthesis of novel materials (optical imaging devices, liquid crystals, ferromagnetic compounds).

Durable electrooptic devices comprising ionic liquids

DOEpatents

Warner, Benjamin P [Los Alamos, NM; McCleskey, T Mark [Los Alamos, NM; Burrell, Anthony K [Los Alamos, NM

2006-10-10

Electrolyte solutions for electrochromic devices such as rear view mirrors and displays with low leakage currents are prepared using inexpensive, low conductivity conductors. Preferred electrolytes include bifunctional redox dyes and molten salt solvents with enhanced stability toward ultraviolet radiation. The solvents include lithium or quaternary ammonium cations, and perfluorinated sulfonylimide anions selected from trifluoromethylsulfonate (CF.sub.3SO.sub.3.sup.-), bis(trifluoromethylsulfonyl)imide ((CF.sub.3SO.sub.2).sub.2N.sup.-), bis(perfluoroethylsulfonyl)imide ((CF.sub.3CF.sub.2SO.sub.2).sub.2N.sup.-) and tris(trifluoromethylsulfonyl)methide ((CF.sub.3SO.sub.2).sub.3C.sup.-). Electroluminescent, electrochromic and photoelectrochromic devices with nanostructured electrodes include ionic liquids with bifunctional redox dyes.

Cause and pre-alarm control of bulking and foaming by Microthrix parvicella--a case study in triple oxidation ditch at a wastewater treatment plant.

PubMed

Xie, B; Dai, X-C; Xu, Y-T

2007-05-08

The cause and control of foaming and bulking in triple oxidation ditch at a wastewater treatment plant (WWTP) were investigated. The results showed that the foaming and bulking was mainly caused by the excessive propagation of Microthrix parvicella, and mostly occurred in the cold winter and spring. Batch and continuous flow experiments indicated that biological techniques such as reducing sludge retention time (SRT) and increasing F/M ratio, chemical methods such as addition of chlorine (NaOCl), quaternary ammonium salt (QAS), or cationic polyacrylamide flocculants (PAM), polyaluminum salt (PAC) could decrease Sludge Volume Index (SVI) and control foaming and bulking at different levels. In practical application, the shorter SRT was effective to control foaming and bulking in initial stage, although it took longer time. Addition of 10gClkgMLSSd(-1) could gradually change the activated sludge with serious foaming and bulking to normal state within a week. Pre-alert control strategies should be established for the control of filamentous foaming and bulking.

Ion Dynamics in a Mixed-Cation Alkoxy-Ammonium Ionic Liquid Electrolyte for Sodium Device Applications.

PubMed

Pope, Cameron R; Kar, Mega; MacFarlane, Douglas R; Armand, Michel; Forsyth, Maria; O'Dell, Luke A

2016-10-18

The ion dynamics in a novel sodium-containing room-temperature ionic liquid (IL) consisting of an ether-functionalised quaternary ammonium cation and bis(trifluoromethylsulfonyl)amide [NTf 2 ] anion with various concentrations of Na[NTf 2 ] have been characterised using differential scanning calorimetry, impedance spectroscopy, diffusometry and NMR relaxation measurements. The IL studied has been specifically designed to dissolve a relatively large concentration of Na[NTf 2 ] salt (over 2 mol kg -1 ) as this has been shown to improve ion transport and conductivity. Consistent with other studies, the measured ionic conductivity and diffusion coefficients show that the overall ionic mobility decreases with decreasing temperature and increasing salt content. NMR relaxation measurements provide evidence for correlated dynamics between the ether-functionalised ammonium and Na cations, possibly with the latter species acting as cross-links between multiple ammonium cations. Finally, preliminary cyclic voltammetry experiments show that this IL can undergo stable electrochemical cycling and could therefore be potentially useful as an electrolyte in a Na-based device. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evaluation of ERTS-1 data applications to geologic mapping, structural analysis and mineral resource inventory of South America with special emphasis on the Andes Mountain region

NASA Technical Reports Server (NTRS)

Carter, W. D. (Principal Investigator)

1973-01-01

The author has identified the following significant results. Segerstrom delineated many grabens (down-faulted blocks) not shown on published maps of Argentina nor of South America. The faults that border the grabens are better appreciated in ERTS-1 imagery than on air photos or on the ground because of the masking affect of alluvial fill deposits. In frame no. 1188-13545 a change in local prevailing wind direction from east to southeast is noted in sand streams. In frame no. 1188-13551 it was surprising to see that Solar del Hombre Muerto was covered with water. In November 1971 the investigator has driven across the salt pan several times without wetting his wheels. It was also possible to differentiate the following rock and soil classes: Granites, metamorphic, volcanic rocks, Tertiary and Quaternary clastic deposits and salt pans. Portions of railroads and highways as well as small towns were identified. In frame no. 1188-13551 the Incahuasi Gold Mine and the Tincalayu Borax Mine were located.

Salt lake Laguna de Fuente de Piedra (S-Spain) as Late Quaternary palaeoenvironmental archive

NASA Astrophysics Data System (ADS)

Höbig, Nicole; Melles, Martin; Reicherter, Klaus

2014-05-01

This study deals with Late Quaternary palaeoenvironmental variability in Iberia reconstructed from terrestrial archives. In southern Iberia, endorheic basins of the Betic Cordilleras are relatively common and contain salt or fresh-water lakes due to subsurface dissolution of Triassic evaporites. Such precipitation or ground-water fed lakes (called Lagunas in Spanish) are vulnerable to changes in hydrology, climate or anthropogenic modifications. The largest Spanish salt lake, Laguna de Fuente de Piedra (Antequera region, S-Spain), has been investigated and serves as a palaeoenvironmental archive for the Late Pleistocene to Holocene time interval. Several sediment cores taken during drilling campaigns in 2012 and 2013 have revealed sedimentary sequences (up to 14 m length) along the shoreline. A multi-proxy study, including sedimentology, geochemistry and physical properties (magnetic susceptibility) has been performed on the cores. The sedimentary history is highly variable: several decimetre thick silty variegated clay deposits, laminated evaporites, and even few-centimetre thick massive gypsum crystals (i.e., selenites). XRF analysis was focussed on valuable palaeoclimatic proxies (e.g., S, Zr, Ti, and element ratios) to identify the composition and provenance of the sediments and to delineate palaeoenvironmental conditions. First age control has been realized by AMS-radiocarbon dating. The records start with approximately 2-3 m Holocene deposits and reach back to the middle of MIS 3 (GS-3). The sequences contain changes in sedimentation rates as well as colour changes, which can be summarized as brownish-beige deposits at the top and more greenish-grey deposits below as well as highly variegated lamination and selenites below ca. 6 m depth. The Younger Dryas, Bølling/Allerød, and the so-called Mystery Interval/Last Glacial Maximum have presumably been identified in the sediment cores and aligned to other climate records. In general, the cores of the Laguna de Fuente de Piedra show cyclic deposition including evaporitic sequences throughout the Holocene and Late Pleistocene, indicating higher fluxes and reworking of organic/inorganic carbon as well as other indicative proxy elements like Ti, Zr and Ca/Sr ratio during Late Pleistocene times. In order to achieve a better understanding of the palaeoenvironmental history in the study area further studies are planned which encompass biological/palaeontological indicators (e.g., pollen, diatoms) as well as another geochemical isotopic techniques on evaporitic deposits such as fluid inclusion analysis.

TETRAHALOINDATE(III)-BASED IONIC LIQUIDS IN THE COUPLING REACTION OF CARBON DIOXIDE AND EPOXIDES TO GENERATE CYCLIC CARBONATES: H-BONDING AND MECHANISTIC STUDIES

EPA Science Inventory

The microwave reactions of InX₃ with [Q]Y produce a series of tetrahaloindate(III)-based ionic liquids (ILs) with a general formula of [Q][InX₃Y] (Q = imidazolium, phosphonium, ammonium, and pyridinium; X = Cl, Br, I; Y = Cl, Br). The reaction of CO₂

Effects of targeting moiety, linker, bifunctional chelator, and molecular charge on biological properties of 64Cu-labeled triphenylphosphonium cations.

PubMed

Kim, Young-Seung; Yang, Chang-Tong; Wang, Jianjun; Wang, Lijun; Li, Zi-Bo; Chen, Xiaoyuan; Liu, Shuang

2008-05-22

In this report, we present the synthesis and evaluation of six new 64Cu-labeled triphenylphosphonium (TPP) cations. Biodistribution studies were performed using the athymic nude mice bearing U87MG human glioma xenografts to explore the impact of TPP moieties, linkers, bifunctional chelators (BFCs), and molecular charge on biological properties of 64Cu radiotracers. On the basis of the results from this study, it is concluded that (1) mTPP (tris(4-methoxyphenyl)phosphonium) is a better mitochondrion-targeting molecule than TPP and 3mTPP (tris(2,4,6-trimethoxyphenyl)phosphonium); (2) DO3A (1,4,7,10-tetraazacyclododecane-4,7,10-triacetic acid) and DO2A (1,4,7,10-tetraazacyclododecane-4,7-diacetic acid) are suitable BFCs for the 64Cu-labeling of TPP cations; (3) NOTA-Bn ( S-2-(4-thioureidobenzyl)-1,4,7-triazacyclononane-1,4,7-triacetic acid) has a significant adverse effect on the radiotracer tumor uptake and tumor-to-background ratios; and (4) monoanionic BFCs should be avoided to ensure that 64Cu chelate has a neutral or negative charge. Considering the tumor uptake and tumor/liver ratios, 64Cu(DO2A-xy-TPP)+ is the best candidate for more extensive evaluations in different tumor-bearing animal models.

Petroleum exploration contribution to the structural history of Golfe du Lin

DOE Office of Scientific and Technical Information (OSTI.GOV)

Curnelle, R.

1988-08-01

Petroleum exploration has strongly contributed to the knowledge of the post-Hercynian structural history of the Golfe du Lion. It shows three stages: (1) Pyrenean orogenesis which started in the Late Cretaceous and culminated during the Eocene (40-75 Ma), (2) Oligocene rifting associated with the oceanic accretion of the Provencal basin, and (3) post-Messinian deformations due to salt tectonics. Pyrenean deformation of the area seems to have been controlled by its Hercynian inheritance: the major transcurrent faults of the Cevenole belt, Nimes, and the Durance. They favored displacement of the deformation in a northeasterly direction along the fault corridors, inside whichmore » the overthrust units were put into place. These east-west-oriented structures show northward vergence. The Pyrenean axial zone in this downthrown part of the belt consist of progressively more northerly units offset by transverse faults. The Oligocene rifting is represented by a series of horsts and deeply subsiding grabens linked to preexisting major faults. The horst are deeply eroded and the Mesozoic carbonates are karstified. The extension of the Messinian evaporitic deposits known throughout the Mediterranean basin is located north of the shallower deep-water well. The gravitational deformation of the salt is expressed by a large number of listric faults which originate in the salt bodies. The sedimentary sequence ends with a thick discordant, erosional, undeformed Pliocene-Quaternary series.« less

Ionic liquids as novel solvents for ionic polymer transducers

NASA Astrophysics Data System (ADS)

Bennett, Matthew D.; Leo, Donald J.

2004-07-01

The use of ionic liquids as solvents for ionic polymer (specifically, Nafion) transducers is demonstrated. Ionic liquids are attractive for this application because of their high inherent stability. Ionic liquids are salts that exist as liquids at room temperature and have no measureable vapor pressure. Therefore, the use of ionic liquids as solvents for ionic polymer transducers can eliminate the traditional problem of water evaporation in these devices. Another benefit of the use of ionic liquids in this way is the reduction or elimination of the characteristic back-relaxation common in water-solvated ionic polymer actuators. The results demonstrate that the viscosity of the ionic liquid and the degree to which the ionic liquid swells the membrane are the important physical parameters to consider. Five ionic liquids were studied, based on substituted pyrrolidinium, phosphonium, or imidazolium cations and fluoroanions. Of these five ionic liquids, transduction is demonstrated in three of them and the best results are obtained with 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ionic liquid. This substance has an electrochemical stability window of 4.1 V, a melting point of -10 °C, and a viscosity of 35-45 cP [19]. Results demonstrate that platinum-plated Nafion transducers solvated with this ionic liquid exhibit sensing and actuation responses and that these transducers are stable in air. Endurance testing of this sample reveals a decrease in the free strain of only 25 % after 250,000 actuation cycles in air.

In vitro antibacterial activity of a novel resin-based pulp capping material containing the quaternary ammonium salt MAE-DB and Portland cement.

PubMed

Yang, Yanwei; Huang, Li; Dong, Yan; Zhang, Hongchen; Zhou, Wei; Ban, Jinghao; Wei, Jingjing; Liu, Yan; Gao, Jing; Chen, Jihua

2014-01-01

Vital pulp preservation in the treatment of deep caries is challenging due to bacterial infection. The objectives of this study were to synthesize a novel, light-cured composite material containing bioactive calcium-silicate (Portland cement, PC) and the antimicrobial quaternary ammonium salt monomer 2-methacryloxylethyl dodecyl methyl ammonium bromide (MAE-DB) and to evaluate its effects on Streptococcus mutans growth in vitro. The experimental material was prepared from a 2 : 1 ratio of PC mixed with a resin of 2-hydroxyethylmethacrylate, bisphenol glycerolate dimethacrylate, and triethylene glycol dimethacrylate (4 : 3 : 1) containing 5 wt% MAE-DB. Cured resin containing 5% MAE-DB without PC served as the positive control material, and resin without MAE-DB or PC served as the negative control material. Mineral trioxide aggregate (MTA) and calcium hydroxide (Dycal) served as commercial controls. S. mutans biofilm formation on material surfaces and growth in the culture medium were tested according to colony-forming units (CFUs) and metabolic activity after 24 h incubation over freshly prepared samples or samples aged in water for 6 months. Biofilm formation was also assessed by Live/Dead staining and scanning electron microscopy. S. mutans biofilm formation on the experimental material was significantly inhibited, with CFU counts, metabolic activity, viability staining, and morphology similar to those of biofilms on the positive control material. None of the materials affected bacterial growth in solution. Contact-inhibition of biofilm formation was retained by the aged experimental material. Significant biofilm formation was observed on MTA and Dycal. The synthesized material containing HEMA-BisGMA-TEGDMA resin with MAE-DB as the antimicrobial agent and PC to support mineralized tissue formation inhibited S. mutans biofilm formation even after aging in water for 6 months, but had no inhibitory effect on bacteria in solution. Therefore, this material shows promise as a pulp capping material for vital pulp preservation in the treatment of deep caries.

Synthesis and Solution Properties of Adamantane Containing Quaternary Ammonium Salt-type Cationic Surfactants: Hydrocarbon-based, Fluorocarbonbased and Bola-type.

PubMed

Yoshimura, Tomokazu; Okada, Mari; Matsuoka, Keisuke

2016-10-01

Quaternary ammonium salt-type cationic surfactants with an adamantyl group (hydrocarbon-type; C n AdAB, fluorocarbon-type; C m F C 3 AdAB, bola-type; Ad-s-Ad, where n, m and s represent hydrocarbon chain lengths of 8-16, fluorocarbon chain lengths of 4-8, and spacer chain length of 10-12) were synthesized via quaternization of N, N-dimethylaminoadamantane and n-alkyl bromide or 1, n-dibromoalkane. Conductivity and surface tension were measured to characterize the solution properties of the synthesized adamantyl group-containing cationic surfactants. In addition, the effects of hydrocarbon and fluorocarbon chain lengths and spacer chain length between headgroups on the measured properties were evaluated by comparison with those of conventional cationic surfactants. The critical micelle concentration (CMC) of C n AdAB and Ad-s-Ad was 2/5 of that for the corresponding conventional surfactants C n TAB and bola-type surfactants with similar number of carbons in the alkyl or alkylene chain; this was because of the increased hydrophobicity due to the adamantyl group. A linear relationship between the logarithm of CMC and the hydrocarbon chain length for C n AdAB was observed, as well as for C n TAB. The slope of the linear correlation for both surfactants was almost the same, indicating that the adamantyl group does not affect the CMC with variations in the hydrocarbon chain length. Similar to conventional surfactants C n TAB, the hydrocarbon-type C n AdAB is highly efficient in reducing the surface tension of water, despite the large occupied area per molecule resulting from the relatively bulky structure of the adamantane skeleton. On the other hand, the bola-type Ad-s-Ad resulted in increased surface tension compared to C n AdAB, indicating that the curved chain between adamantyl groups leads to poor adsorption and orientation at the air-water interface.

Novel Quaternary Quantum Decoder, Multiplexer and Demultiplexer Circuits

NASA Astrophysics Data System (ADS)

Haghparast, Majid; Monfared, Asma Taheri

2017-05-01

Multiple valued logic is a promising approach to reduce the width of the reversible or quantum circuits, moreover, quaternary logic is considered as being a good choice for future quantum computing technology hence it is very suitable for the encoded realization of binary logic functions through its grouping of 2-bits together into quaternary values. The Quaternary decoder, multiplexer, and demultiplexer are essential units of quaternary digital systems. In this paper, we have initially designed a quantum realization of the quaternary decoder circuit using quaternary 1-qudit gates and quaternary Muthukrishnan-Stroud gates. Then we have presented quantum realization of quaternary multiplexer and demultiplexer circuits using the constructed quaternary decoder circuit and quaternary controlled Feynman gates. The suggested circuits in this paper have a lower quantum cost and hardware complexity than the existing designs that are currently used in quaternary digital systems. All the scales applied in this paper are based on Nanometric area.

Toward a Modular Ionic Liquid Platform for the Custom Design of Energetic Materials: Understanding How the Dual Nature of Ionic Liquids Relates Key Physical Properties to Target Structures

DTIC Science & Technology

2009-11-30

cations were obtained and isolated with a diverse group of azolate anions including nitro- substituted benzotriazolate, benzimidazolate , 1,2,4-triazolate... benzimidazolate , or benzotrizolate) have received much less attention than those containing azolium cations, although more results are now starting to...phosphonium cations combined with energetically-substituted tetrazolate, triazolate, imidazolate, benzimidazolate , and benzotriazolate anions (Figure

Evaluation of textiles proposed for spacecraft crew apparel

NASA Technical Reports Server (NTRS)

Duncan, W. C.

1976-01-01

Textiles proposed for spacecraft wearing apparel were tested for possible primary irritancy and allergenicity using guinea pigs and human subjects. The materials submitted for testing were: (1) blue, loosely knit fabric of a copolymer of chlorotrifluoroethylene and ethylene (CTFE), (2) a white fabric, 100% cotton double knit, treated with fire retardant Tetrakis (hydroxymethyl) phosphonium hydroxide/ammonia, and (3) a gold colored polyimide fabric. There were no adverse reactions to any of the fabrics.

Improvement of lipophilicity and membrane transport of cefuroxime using in vitro models.

PubMed

Mrestani, Yahya; Mrestani-Klaus, Carmen; Bretschneider, Beate; Neubert, Reinhard H H

2004-11-01

Most beta-lactam antibiotics cannot be absorbed orally and, therefore, must be administered intravenously (i.v.) or intramuscularly (i.m.). Because of the obvious drawbacks of drug delivery by injection, the development of alternatives with enhanced oral bioavailability is receiving much attention in pharmaceutical research. Cefuroxime exhibiting significant advantages in the parental treatment of common infections, was used as model drug in the present study. The effect of the cationic absorption enhancers (four quaternary ammonium salts) on the lipophilicity of cefuroxime was investigated by means of the n-octanol/water system. The results on partitioning coefficients in the n-octanol/buffer system were confirmed using an in vitro transport model with artificial (dodecanol collodium membrane) and biological membranes (Charles-River guinea pig).

The Agost Basin (Betic Cordillera, Alicante province, Spain): a pull-apart basin involving salt tectonics

NASA Astrophysics Data System (ADS)

Martín-Martín, Manuel; Estévez, Antonio; Martín-Rojas, Ivan; Guerrera, Francesco; Alcalá, Francisco J.; Serrano, Francisco; Tramontana, Mario

2018-03-01

The Agost Basin is characterized by a Miocene-Quaternary shallow marine and continental infilling controlled by the evolution of several curvilinear faults involving salt tectonics derived from Triassic rocks. From the Serravallian on, the area experienced a horizontal maximum compression with a rotation of the maximum stress axis from E-W to N-S. The resulting deformation gave rise to a strike-slip fault whose evolution is characterized progressively by three stages: (1) stepover/releasing bend with a dextral motion of blocks; (2) very close to pure horizontal compression; and (3) restraining bend with a sinistral movement of blocks. In particular, after an incipient fracturing stage, faults generated a pull-apart basin with terraced sidewall fault and graben subzones developed in the context of a dextral stepover during the lower part of late Miocene p.p. The occurrence of Triassic shales and evaporites played a fundamental role in the tectonic evolution of the study area. The salty material flowed along faults during this stage generating salt walls in root zones and salt push-up structures at the surface. During the purely compressive stage (middle part of late Miocene p.p.) the salt walls were squeezed to form extrusive mushroom-like structures. The large amount of clayish and salty material that surfaced was rapidly eroded and deposited into the basin, generating prograding fan clinoforms. The occurrence of shales and evaporites (both in the margins of the basin and in the proper infilling) favored folding of basin deposits, faulting, and the formation of rising blocks. Later, in the last stage (upper part of late Miocene p.p.), the area was affected by sinistral restraining conditions and faults must have bent to their current shape. The progressive folding of the basin and deformation of margins changed the supply points and finally caused the end of deposition and the beginning of the current erosive systems. On the basis of the interdisciplinary results, the Agost Basin can be considered a key case of the interference between salt tectonics and the evolution of strike-slip fault zones. The reconstructed model has been compared with several scaled sandbox analogical models and with some natural pull-apart basins.

Structure and transport properties of a plastic crystal ion conductor: diethyl(methyl)(isobutyl)phosphonium hexafluorophosphate.

PubMed

Jin, Liyu; Nairn, Kate M; Forsyth, Craig M; Seeber, Aaron J; MacFarlane, Douglas R; Howlett, Patrick C; Forsyth, Maria; Pringle, Jennifer M

2012-06-13

Understanding the ion transport behavior of organic ionic plastic crystals (OIPCs) is crucial for their potential application as solid electrolytes in various electrochemical devices such as lithium batteries. In the present work, the ion transport mechanism is elucidated by analyzing experimental data (single-crystal XRD, multinuclear solid-state NMR, DSC, ionic conductivity, and SEM) as well as the theoretical simulations (second moment-based solid static NMR line width simulations) for the OIPC diethyl(methyl)(isobutyl)phosphonium hexafluorophosphate ([P(1,2,2,4)][PF(6)]). This material displays rich phase behavior and advantageous ionic conductivities, with three solid-solid phase transitions and a highly "plastic" and conductive final solid phase in which the conductivity reaches 10(-3) S cm(-1). The crystal structure shows unique channel-like packing of the cations, which may allow the anions to diffuse more easily than the cations at lower temperatures. The strongly phase-dependent static NMR line widths of the (1)H, (19)F, and (31)P nuclei in this material have been well simulated by different levels of molecular motions in different phases. Thus, drawing together of the analytical and computational techniques has allowed the construction of a transport mechanism for [P(1,2,2,4)][PF(6)]. It is also anticipated that utilization of these techniques will allow a more detailed understanding of the transport mechanisms of other plastic crystal electrolyte materials.

Effect of Structure on Transport Properties (Viscosity, Ionic Conductivity, and Self-Diffusion Coefficient) of Aprotic Heterocyclic Anion (AHA) Room Temperature Ionic Liquids. 2. Variation of Alkyl Chain Length in the Phosphonium Cation.

PubMed

Sun, Liyuan; Morales-Collazo, Oscar; Xia, Han; Brennecke, Joan F

2016-06-30

A series of room-temperature ionic liquids (ILs) composed of triethyl(alkyl)phosphonium cations paired with three different aprotic heterocyclic anions (AHAs) (alkyl = butyl ([P2224](+)) and octyl ([P2228](+))) were prepared to investigate the effect of cationic alkyl chain length on transport properties. The transport properties and density of these ILs were measured from 283.15 to 343.15 K at ambient pressure. The dependence of the transport properties (viscosity, ionic conductivity, diffusivity, and molar conductivity) on temperature can be described by the Vogel-Fulcher-Tamman (VFT) equation. The ratio of the molar conductivity obtained from the molar concentration and ionic conductivity measurements to that calculated from self-diffusion coefficients (measured by pulsed gradient spin-echo nuclear magnetic resonance spectroscopy) using the Nernst-Einstein equation was used to quantify the ionicity of these ILs. The molar conductivity ratio decreases with increasing number of carbon atoms in the alkyl chain, indicating that the reduced Coulombic interactions resulting from lower density are more than balanced by the increased van der Waals interactions between the alkyl chains. The results of this study may provide insight into the design of ILs with enhanced dynamics that may be suitable as electrolytes in lithium ion batteries and other electrochemical applications.

Determination of gas-liquid partition coefficients of several organic solutes in trihexyl(tetradecyl)phosphonium bromide using capillary gas chromatography columns.

PubMed

Ronco, Nicolás R; Menestrina, Fiorella; Romero, Lílian M; Castells, Cecilia B

2017-06-09

In this paper, we report gas-liquid partition constants for thirty-five volatile organic solutes in the room temperature ionic liquid trihexyl(tetradecyl)phosphonium bromide measured by gas-liquid chromatography using capillary columns. The relative contribution of gas-liquid partition and interfacial adsorption to retention was evaluated through the use of columns with different the phase ratio. Four capillary columns with exactly known phase ratios were constructed and employed to measure the solute retention factors at four temperatures between 313.15 and 343.15K. The partition coefficients were calculated from the slopes of the linear regression between solute retention factors and the reciprocal of phase ratio at a given temperature according to the gas-liquid chromatographic theory. Gas-liquid interfacial adsorption was detected for a few solutes and it has been considered for the calculations of partition coefficient. Reliable solute's infinite dilution activity coefficients can be obtained when retention data are determined by a unique partitioning mechanism. The partial molar excess enthalpies at infinite dilution have been estimated from the dependence of experimental values of solute activity coefficients with the column temperature. A thorough discussion of the uncertainties of the experimental measurements and the main advantages of the use of capillary columns to acquire the aforementioned relevant thermodynamic information was performed. Copyright © 2017 Elsevier B.V. All rights reserved.

Multicomponent homogeneous alloys and method for making same

DOEpatents

Dutta, Partha S.; Miller, Thomas R.

2003-09-02

The present application discloses a method for preparing a homogeneous ternary or quaternary alloy from a quaternary melt. The method includes providing a family of phase diagrams for the quaternary melt which shows (i) composition/temperature data, (ii) tie lines connecting equilibrium liquid and solid compositions, and (iii) isotherms representing boundaries of a miscibility gap. Based on the family of phase diagrams, a quaternary melt composition and an alloy growth temperature is selected. A quaternary melt having the selected quaternary melt composition is provided and a ternary or quaternary alloy is grown from the quaternary melt at the selected alloy growth temperature. A method for making homogeneous ternary or quaternary alloy from a ternary or quaternary melt is also disclosed, as are homogeneous quaternary single-crystal alloys which are substantially free from crystal defects and which have the formula A.sub.x B.sub.1-x C.sub.y D.sub.1-y, x and y being the same or different and in the range of 0.001 to 0.999.

On the origins of hypersaline groundwater in the Nile Delta aquifer

NASA Astrophysics Data System (ADS)

van Engelen, Joeri; Oude Essink, Gualbert H. P.; Kooi, Henk; Bierkens, Marc F. P.

2018-05-01

The Nile Delta is essential to Egypt's agro- and socio-economy. Although surface water is the traditional source for Egypt's irrigation, the shallow fresh groundwater resources underlying the delta are increasingly burdened by groundwater pumping, which increases interest in the status of the groundwater resources. Groundwater up to three times more saline than sea water was found at 600 m depth. The occurrence of this hypersaline groundwater raises doubts on the often-made assumption in the literature that seawater is the only source of salt in the Nile Delta aquifer and makes further investigation necessary. Knowledge on the origin of this hypersaline groundwater is key in assessing the possibility of deep fresh groundwater pockets. In this paper we conducted computational analyses to assess possible origins using both analytical solutions and numerical models. It is concluded that the hypersaline groundwater can either originate from Quaternary free convection systems, or from compaction-induced upward salt transport of hypersaline groundwater that formed during the Messinian salinity crisis. Our results also indicate that with groundwater dating it is possible to discriminate between these two hypotheses. Furthermore, it is deduced that the hydrological connection between aquifer and sea is crucial to the hydrogeological functioning of the Nile Delta Aquifer.

Spiro-(1,1‧)-bipyrrolidinium tetrafluoroborate salt as high voltage electrolyte for electric double layer capacitors

NASA Astrophysics Data System (ADS)

Yu, Xuewen; Ruan, Dianbo; Wu, Changcheng; Wang, Jing; Shi, Zhiqiang

2014-11-01

A novel quaternary ammonium salt based on spiro-(1,1‧)-bipyrolidinium tetrafluoroborate (SBP-BF4) has been synthesized and dissolved in propylene carbonate (PC) with 1.5 mol L-1 (M) concentration for electric double-layer capacitors (EDLCs). The physic-chemical properties and electrochemical performance of SBP-BF4/PC electrolyte are investigated. Compared with the standard electrolyte 1.5 M TEMA-BF4 in PC, the novel SBP-BF4/PC electrolyte exhibited much better electrochemical performance due to its smaller cation size, lower viscosity and higher conductivity. The specific discharge capacitance of activated carbon electrode based EDLCs using SBP-BF4/PC electrolyte is 120 F g-1, the energy density and power density can reach 31 kW kg-1 and 6938 W kg-1, respectively, when the working voltage is 2.7 V and current density is 50 mA g-1. The withstand voltage of activated carbon based EDLCs with SBP-BF4/PC electrolyte can reach to 3.2 V, where the stable discharge capacitance and energy density are 121 F g-1 and 43 Wh kg-1, respectively.

Comparative analyses of quaternary arrangements in homo-oligomeric proteins in superfamilies: Functional implications.

PubMed

Sudha, Govindarajan; Srinivasan, Narayanaswamy

2016-09-01

A comprehensive analysis of the quaternary features of distantly related homo-oligomeric proteins is the focus of the current study. This study has been performed at the levels of quaternary state, symmetry, and quaternary structure. Quaternary state and quaternary structure refers to the number of subunits and spatial arrangements of subunits, respectively. Using a large dataset of available 3D structures of biologically relevant assemblies, we show that only 53% of the distantly related homo-oligomeric proteins have the same quaternary state. Considering these homologous homo-oligomers with the same quaternary state, conservation of quaternary structures is observed only in 38% of the pairs. In 36% of the pairs of distantly related homo-oligomers with different quaternary states the larger assembly in a pair shows high structural similarity with the entire quaternary structure of the related protein with lower quaternary state and it is referred as "Russian doll effect." The differences in quaternary state and structure have been suggested to contribute to the functional diversity. Detailed investigations show that even though the gross functions of many distantly related homo-oligomers are the same, finer level differences in molecular functions are manifested by differences in quaternary states and structures. Comparison of structures of biological assemblies in distantly and closely related homo-oligomeric proteins throughout the study differentiates the effects of sequence divergence on the quaternary structures and function. Knowledge inferred from this study can provide insights for improved protein structure classification and function prediction of homo-oligomers. Proteins 2016; 84:1190-1202. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Substituted Quaternary Ammonium Salts Improve Low-Temperature Performance of Double-Layer Capacitors

NASA Technical Reports Server (NTRS)

Brandon, Erik J.; Smart, Marshall C.; West, William C.

2011-01-01

Double-layer capacitors are unique energy storage devices, capable of supporting large current pulses as well as a very high number of charging and discharging cycles. The performance of doublelayer capacitors is highly dependent on the nature of the electrolyte system used. Many applications, including for electric and fuel cell vehicles, back-up diesel generators, wind generator pitch control back-up power systems, environmental and structural distributed sensors, and spacecraft avionics, can potentially benefit from the use of double-layer capacitors with lower equivalent series resistances (ESRs) over wider temperature limits. Higher ESRs result in decreased power output, which is a particular problem at lower temperatures. Commercially available cells are typically rated for operation down to only 40 C. Previous briefs [for example, Low Temperature Supercapacitors (NPO-44386), NASA Tech Briefs, Vol. 32, No. 7 (July 2008), p. 32, and Supercapacitor Electrolyte Solvents With Liquid Range Below 80 C (NPO-44855), NASA Tech Briefs, Vol. 34, No. 1 (January 2010), p. 44] discussed the use of electrolytes that employed low-melting-point co-solvents to depress the freezing point of traditional acetonitrile-based electrolytes. Using these modified electrolyte formulations can extend the low-temperature operational limit of double-layer capacitors beyond that of commercially available cells. This previous work has shown that although the measured capacitance is relatively insensitive to temperature, the ESR can rise rapidly at low temperatures, due to decreased electrolyte conductance within the pores of the high surface- area carbon electrodes. Most of these advanced electrolyte systems featured tetraethylammonium tetrafluoroborate (TEATFB) as the salt. More recent work at JPL indicates the use of the asymmetric quaternary ammonium salt triethylmethylammonium tetrafluoroborate (TEMATFB) or spiro-(l,l')-bipyrrolidium tetrafluoroborate (SBPBF4) in a 1:1 by volume solvent mixture of acetonitrile (AN) and methyl formate (MF) enables double-layer capacitor cells to operate well below -40 C with a relatively low ESR. Typically, a less than twofold increase in ESR is observed at -65 C relative to room-temperature values, when these modified electrolyte blends are used in prototype cells. Double-layer capacitor coin cells filled with these electrolytes have displayed the lowest measured ESR for an organic electrolyte to date at low temperature (based on a wide range of electrolyte screening studies at JPL). The cells featured high-surface-area (approximately equal to 2,500 m/g) carbon electrodes that were 0.50 mm thick and 1.6 cm in diameter, and coated with a thin layer of platinum to reduce cell resistance. A polyethylene separator was used to electrically isolate the electrodes.

Electrospray ionization tandem mass spectrometry of ammonium cationized polyethers.

PubMed

Nasioudis, Andreas; Heeren, Ron M A; van Doormalen, Irene; de Wijs-Rot, Nicolette; van den Brink, Oscar F

2011-05-01

Quaternary ammonium salts (Quats) and amines are known to facilitate the MS analysis of high molar mass polyethers by forming low charge state adduct ions. The formation, stability, and behavior upon collision-induced dissociation (CID) of adduct ions of polyethers with a variety of Quats and amines were studied by electrospray ionization quadrupole time-of-flight, quadrupole ion trap, and linear ion trap tandem mass spectrometry (MS/MS). The linear ion trap instrument was part of an Orbitrap hybrid mass spectrometer that allowed accurate mass MS/MS measurements. The Quats and amines studied were of different degree of substitution, structure, and size. The stability of the adduct ions was related to the structure of the cation, especially the amine's degree of substitution. CID of singly/doubly charged primary and tertiary ammonium cationized polymers resulted in the neutral loss of the amine followed by fragmentation of the protonated product ions. The latter reveals information about the monomer unit, polymer sequence, and endgroup structure. In addition, the detection of product ions retaining the ammonium ion was observed. The predominant process in the CID of singly charged quaternary ammonium cationized polymers was cation detachment, whereas their doubly charged adduct ions provided the same information as the primary and tertiary ammonium cationized adduct ions. This study shows the potential of specific amines as tools for the structural elucidation of high molar mass polyethers. © American Society for Mass Spectrometry, 2011

Potentiostatic control of ionic liquid surface film formation on ZE41 magnesium alloy.

PubMed

Efthimiadis, Jim; Neil, Wayne C; Bunter, Andrew; Howlett, Patrick C; Hinton, Bruce R W; MacFarlane, Douglas R; Forsyth, Maria

2010-05-01

The generation of potentially corrosion-resistant films on light metal alloys of magnesium have been investigated. Magnesium alloy, ZE41 [Mg-Zn-Rare Earth (RE)-Zr, nominal composition approximately 4 wt % Zn, approximately 1.7 wt % RE (Ce), approximately 0.6 wt % Zr, remaining balance, Mg], was exposed under potentiostatic control to the ionic liquid trihexyl(tetradecyl)phosphonium diphenylphosphate, denoted [P(6,6,6,14)][DPP]. During exposure to this IL, a bias potential, shifted from open circuit, was applied to the ZE41 surface. Electrochemical impedance spectroscopy (EIS) and chronoamperometry (CA) were used to monitor the evolution of film formation on the metal surface during exposure. The EIS data indicate that, of the four bias potentials examined, applying a potential of -200 mV versus OCP during the exposure period resulted in surface films of greatest resistance. Both EIS measurements and scanning electron microscopy (SEM) imaging indicate that these surfaces are substantially different to those formed without potential bias. Time of flight-secondary ion mass spectrometry (ToF-SIMS) elemental mapping of the films was utilized to ascertain the distribution of the ionic liquid cationic and anionic species relative to the microstructural surface features of ZE41 and indicated a more uniform distribution compared with the surface following exposure in the absence of a bias potential. Immersion of the treated ZE41 specimens in a chloride contaminated salt solution clearly indicated that the ionic liquid generated surface films offered significant protection against pitting corrosion, although the intermetallics were still insufficiently protected by the IL and hence favored intergranular corrosion processes.

The "DREAM" IODP project to drill the Mediterranean Salt Giant on the Balearic Promontory

NASA Astrophysics Data System (ADS)

Lofi, Johanna; Camerlenghi, Angelo; Aloisi, Giovanni; Maillard, Agnès; Garcia-Castellanos, Daniel; Huebscher, Christian; Kuroda, Junichiro

2017-04-01

Salt giants preserving kilometer-thick evaporite layers are the sedimentary expression of extreme environmental events of global relevance. Despite their global occurrence and general importance on Earth, there is currently no complete stratigraphic record through an un-deformed salt giant of marine origin. Similarly, there is a significant lack of knowledge about the factors controlling salt giants deposition, their early evolution, the impact they exert on the isostatic response of continental margins and on sub-salt formations, and the unprecedented deep biosphere they may harbor. The Mediterranean Messinian salt giant, which formed 5.5 Myrs ago, is one of the youngest salt giant on Earth and is currently lying below the Plio-Quaternary cover in a relatively un-deformed state close to its original depositional configuration. This salt giant is thus accessible by drilling and forms an ideal case study that could be used as a reference for older salt giants. However, since its discovery in 1970 during the DSDP Leg XIII, and despite 40 years or multi-disciplinary researches, this salt giant is still not fully understood and remains one of the longest-living controversies in Earth Science. In this context, the IODP DREAM project aims at exploring the Mediterranean salt giant by drilling with the JOIDES Resolution a transect of 4 sites on the southern margin of the Balearic promontory (Western Mediterranean). We identified this area as likely the only place in the Mediterranean where we could implement a shallow-to-deep transect of non-riser drilling sites. Due to the geological history and pre-structuration of the Promontory, MSC deposits are found preserved in a series of sedimentary basins lying at different water depths between the present-day coastline and the deep central salt basins. DREAM thus offers a unique opportunity to sample several hundred of meters of material forming the Mediterranean salt giant in varied water depths. This unique sedimentary record should allow testing 1) the contradictory emplacement models that explain its genesis and 2) the presence of halophilic micro-organisms it may host/feed. DREAM is a part of a bigger Multi-phase IODP Drilling Project entitled "Uncovering a Salt Giant" (857-MDP, coord. A. Camerlenghi) born out of a series of workshops and international initiatives carried out since 2014. The DREAM pre-proposal P857B has been accepted by the IODP Science Evaluation Panel in January 2016. The full-proposal will be submitted after the acquisition of complementary Site Survey Data in 2017. The DREAM project is performed in close link with various international initiatives including the COST Action CA15103 and ANR Project MEDSALT (Camerlenghi et al., this congress) and the IMMAGE ICDP-IODP amphibious proposal (Flecker et al., this congress). DREAM co-proponents: J. Anton, M.A. Bassetti, D. Birgel, R. Bourillot, A. Caruso, H. Daigle, G. DeLange, F. Dela Pierre, R. Flecker, V. Gaullier, D. Hodell, F. Jimenez-Espejo, W. Krijgsman, L. Lourens, S. Lugli, V. Manzi, T. McGenity, J. McKenzie, P. Meijer, H. Moreno, A. Moscariello, P. Munch, N. Ohkouchi, J. Peckmann, P. Pezard, J. Poort, M. Roveri, F. Sierro, K. Takai, T. Treude.

Structural Data for the Columbus Salt Marsh Geothermal Area - GIS Data

DOE Data Explorer

Faulds, James E.

2011-12-31

Shapefiles and spreadsheets of structural data, including attitudes of faults and strata and slip orientations of faults. - Detailed geologic mapping of ~30 km2 was completed in the vicinity of the Columbus Marsh geothermal field to obtain critical structural data that would elucidate the structural controls of this field. - Documenting E‐ to ENE‐striking left lateral faults and N‐ to NNE‐striking normal faults. - Some faults cut Quaternary basalts. - This field appears to occupy a displacement transfer zone near the eastern end of a system of left‐lateral faults. ENE‐striking sinistral faults diffuse into a system of N‐ to NNE‐striking normal faults within the displacement transfer zone. - Columbus Marsh therefore corresponds to an area of enhanced extension and contains a nexus of fault intersections, both conducive for geothermal activity.

Colloidal 3-Mercaptopropionic Acid Capped Lead Sulfide Quantum Dots in a Low Boiling Point Solvent.

PubMed

Reinhart, Chase C; Johansson, Erik

2017-04-26

Colloidal 3-mercaptopropionic acid (3-MPA) capped lead sulfide quantum dots were prepared in a variety of organic solvents stabilized with a quaternary ammonium halide salt. The stabilized colloids' optical properties were studied through optical absorption and emission spectroscopy and found to be dependent on both the concentration of a new ligand and stabilizer, and sample age. Nanocrystal ligand chemistry was studied through a combination of 1 H NMR and two-dimensional Nuclear Overhauser Effect Spectroscopy (NOESY) which revealed full displacement of the original oleate ligand to form a dynamically exchanging ligand shell. The colloids were studied optically and via NMR as they aged and revealed a quantitative conversion of monomeric 3-mercaptopropionic acid to its dimer, dithiodipropionic acid (dTdPA).

Towards Tartaric-Acid-Derived Asymmetric Organocatalysts

PubMed Central

Gratzer, Katharina; Gururaja, Guddeangadi N; Waser, Mario

2013-01-01

Tartaric acid is one of the most prominent naturally occurring chiral compounds. Whereas its application in the production of chiral ligands for metal-catalysed reactions has been exhaustively investigated, its potential to provide new organocatalysts has been less extensively explored. Nevertheless, some impressive results, such as the use of TADDOLs as chiral H-bonding catalysts or of tartrate-derived asymmetric quaternary ammonium salt catalysts, have been reported over the last decade. The goal of this article is to provide a representative overview of the potential and the limitations of tartaric acid or TADDOLs in the creation of new organocatalysts and to highlight some of the most spectacular applications of these catalysts, as well as to summarize case studies in which other classes of chiral backbones were better suited. PMID:24194674

A review on acridinylthioureas and its derivatives: biological and cytotoxic activity.

PubMed

Kožurková, Mária; Sabolová, Danica; Kristian, Pavol

2017-10-01

Acridines possess two characteristics that have led many researchers to consider the agents interesting targets for future development as potential farmacophores: the planar acridine skeleton, which is able to intercalate into DNA, and the intense fluorescence of the agents. This review offers a study of the multifunctional character of acridines and the synthesis of novel acridine derivatives, with particular focus being placed on isothiocyanates and their congeners, e.g. thioureas, isothioureas, quaternary ammonium salts and platinum/gold conjugates. The review provides an overview of the structure, spectral properties, DNA binding and biological activity of acridinylthiourea congeners. These acridinylthiourea derivatives display significant cytotoxic activities against different types of cancer cell lines at micromolar concentrations. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

Organic solvents, electrolytes, and lithium ion cells with good low temperature performance

NASA Technical Reports Server (NTRS)

Huang, Chen-Kuo (Inventor); Smart, Marshall C. (Inventor); Surampudi, Subbarao (Inventor); Bugga, Ratnakumar V. (Inventor)

2002-01-01

Multi-component organic solvent systems, electrolytes and electrochemical cells characterized by good low temperature performance are provided. In one embodiment, an improved organic solvent system contains a ternary mixture of ethylene carbonate, dimethyl carbonate and diethyl carbonate. In other embodiments, quaternary systems include a fourth component, i.e, an aliphatic ester, an asymmetric alkyl carbonate or a compound of the formula LiOX, where X is R, COOR, or COR, where R is alkyl or fluoroalkyl. Electrolytes based on such organic solvent systems are also provided and contain therein a lithium salt of high ionic mobility, such as LiPF.sub.6. Reversible electrochemical cells, particularly lithium ion cells, are constructed with the improved electrolytes, and preferably include a carbonaceous anode, an insertion type cathode, and an electrolyte interspersed therebetween.

Preliminary results on quaternary studies from Bajestan Basin (Kavir-e Namak), Iran

NASA Astrophysics Data System (ADS)

Majid Padashi, Seyed; Büdel, Christian; Ullmann, Tobias; Tintrup, Angela; Baumhauer, Roland

2017-04-01

The increasing population and demand for developing infrastructures on the one hand, and the recent issues on water and air quality on the other hand, in addition to droughts and the shrinking of many wetlands and lakes, have encouraged Iran recently to invest more in palaeoenvironmental research - specifically on quaternary basins. Preliminary results of our study through field work, satellite imagery processing, SRTM data analysis and drilling, have created new insights on the Iranian playas and the history of the lakes. A combined geological and geomorphological approach for studying young lakes and playas of Iran has led to the identification of at least five major types of lakes and playas in different parts of Iran; for example the Bajestan basin which ranks the second biggest playa of Iran, is placed in the edge of the central Iranian microplate and Lut structural block. The Bajestan Playa (Kavir-e Namak) is surrounded by cretaceous limestones in the south and Paleozoic formations in the north. The basin comprises several kinds of quaternary deposits including sand dunes and Aeolian deposits, fluvial sediments, alluvial fans and lake sediments. The aeolian activity in the basin is primarily shaping landforms in the southwest and the north of the area. The major fluvial activity is considered to be driven from east and south of the playa. The integration of field observations and data derived from the analysis of SRTM digital elevation model (90m) and Landsat satellite imagery shows that the major part of the playa has flat slope. In addition, the morphometric assessment and the hydrological modelling showed that the major current alluvial channels have SW/NE trend with the highest density and intensity of activity in south west of the basin. The major alluvial deposits in the north and south of the playa represent a dissimilar geomorphology. While the northern part of the basin, from the rock unit outcrops to the edge of playa, is occupied by a narrow alluvial domain, the southern part is dominated by a megafan, with an approximately 3.6 times longer horizontal extension toward the wet zone of the southern rim of the playa lake. According to the satellite images and field observations, this is due to the tectonic activity and to the structural situation, which is causing different shapes of the two sides of the playa. Accordingly, the wet zone in the northern reach of the playa is weakly developed, in opposite to the southern part. Based on cored samples from young deposits of the Bajestan basin, several salt horizons and laminated sediments have be discovered. An initial core description of the core sediments in the lab, led to a classification of salt horizons (based on size, shape and thickness) into three major groups.

Variation of concentration of tetrakis and hydroquinone with post-irradiation times in PAGAT polymer gel dosimeter

NASA Astrophysics Data System (ADS)

Venning, Anthony J.; Hill, Brendan; Baldock, Clive

2006-12-01

Following on from the investigation of the normoxic PAGAT polymer gel dosimeter by Venning A J, Hill B, Brindha S, Healy B J and Baldock C 2005 Phys. Med. Biol. 50 3875-3888 this paper examines the change in transverse relaxation rate R2 with time for different concentrations of tetrakis (hydroxymethyl) phosphonium chloride and hydroquinone for fixed concentrations of N,N-methylene-bis-acrylamide, acrylamide, gelatine and H2M/O.

Generation and detection of the cyclohexadienyl radical in phosphonium ionic liquids.

PubMed

Lauzon, J M; Arseneau, D J; Brodovitch, J C; Clyburne, J A C; Cormier, P; McCollum, B; Ghandi, K

2008-10-21

The formation of the cyclohexadienyl radical, C(6)H(6)Mu, in ionic and molecular solvents has been compared. This is the first time that a muoniated free radical is reported in an ionic liquid. In marked contrast to molecular liquids, free radical generation in ionic liquids is significantly enhanced. Comparison of the hyperfine interactions in the ionic liquid and in molecular solvents and with theoretical calculations, suggests significant and unforeseen solvent interaction with the cyclohexadienyl radical.

Understanding the paleo environment in the Danish North Sea using 2D and 3D seismic analyses

NASA Astrophysics Data System (ADS)

Prins, Lasse K.; Clausen, Ole R.; Andresen, Katrine J.

2017-04-01

This study presents the first detailed and integrated mapping of buried Quaternary valleys, river systems and iceberg scourings from the Danish North Sea region. The mapped features coincide spatially but have very different characteristics and incision levels which allow us to constrain their relative timing and differentiate their environment of formation (subglacial, proglacial and marine). The results of the study bring new critical information regarding the paleoenvironment of the North Sea Basin during the latest Quaternary deglaciation period and our analysis provide a well-tested workflow for utilizing 2D and 3D seismic data in relation to paleogeographical reconstructions. Our analysis is based on interpretation of conventional 3D seismic and high-resolution sparker data from the Southern Danish Central Graben. The project forms part of the portfolio for the 'Danish Hydrocarbon Research and Technology Centre' and aims at building a high-resolution 3D geological-geotechnical model of the shallow subsurface by using geophysical data combined with geological and geotechnical data from shallow borings. One of the objectives is to map potential geohazards for offshore installations such as buried valleys and constrain their geotechnical properties. The central North Sea is known to have been covered by glaciers several times during the Quaternary with climate changing between arctic and boreal. Marine conditions periodically prevailed and large river systems mainly from central Europe dominated during periods of subaerial exposure. Hence, many buried erosional incisions, primarily tunnel valleys but also river systems, can be observed within the upper 200-400 meters of the Quaternary succession throughout the central North Sea region. A high-resolution mapping of the infill of the tunnel valleys and river systems have however not previously been presented. Our analysis shows that within the study area at least four generations of tunnel valley formation and river system incisions can be mapped. The tunnel valleys have a strong NE-SW orientation and are typically characterized by an irregular base. The fluvial river systems which are the youngest, are smaller, typically with an anastomosing appearance. They generally have an NW-SE strike perpendicular to the older tunnel valleys. Clear sedimentary structures can be recognized on the high-resolution 2D seismic data indicating a complex history of cut and fill. In general, the study area displays a very heterogenic sedimentation pattern with varying valley types and significant lateral variations within the same valleys revealing a subtle interplay between incision and infilling. In some areas we furthermore see a distinct control of the river system morphology by deeper salt structures adding to the complexity of controlling factors for the rivers and tunnel valleys in the study area. The results of the study provide valuable information on the evolution of the Quaternary ice-sheets and drainage patterns and hence exemplify the use of seismic data for Quaternary paleo-environmental studies. With the good control on the distribution and infill of buried valleys and river systems, the study furthermore provides the first constrain to a detailed 3D model of different litho-facies based on seismic facies analysis combined with information from shallow borings.

Anion exchange membranes composed of a poly(2,6-dimethyl-1,4-phenylene oxide) random copolymer functionalized with a bulky phosphonium cation

DOE PAGES

Liu, Ye; Zhang, Bingzi; Kinsinger, Corey L.; ...

2016-01-22

A random copolymer, tris(2,4,6-trimethoxyphenyl) phosphonium functionalized poly(2,6-dimethyl-1,4-phenylene oxide) (PPO-TPQP) was cast from three different solvents: dimethyl sulfoxide (DMSO), ethyl lactate, or a 41:59 vol% mixture of DMSO and ethyl lactate. Solvents were selected via analysis of the Hansen solubility parameters to vary the phase separation of the polymer in the films. An optimized mixture of DMSO and ethyl lactate chosen for film fabrication and this film was contrasted with films cast from the neat constituent solvents. Atomic force microscopy identified domains from nanometer to tens of nanometer sizes, while the light microscopy showed features on the order of micron. SAXSmore » revealed a cation scattering peak with a d-spacing from 7 to 15 Å. Trends in conductivity and water diffusion for the membranes vary depending on the solvent from which they are cast. The mixed solvent cast membrane shows a linear Arrhenius behavior indicating fully dissociated cationic/anionic groups, and has the highest bromide conductivity of 3 mS/cm at 95% RH, 90 °C. The ethyl lactate cast membrane shows a linear Arrhenius relation in conductivity, but a Vogel-Tamman-Fulcher behavior in its water self-diffusion. While water increases bromide dissociation, water and bromide transport in these films seems to be decoupled. Lastly, this is particularly true for the film cast from ethyl lactate.« less

Anion exchange membranes composed of a poly(2,6-dimethyl-1,4-phenylene oxide) random copolymer functionalized with a bulky phosphonium cation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Ye; Zhang, Bingzi; Kinsinger, Corey L.

A random copolymer, tris(2,4,6-trimethoxyphenyl) phosphonium functionalized poly(2,6-dimethyl-1,4-phenylene oxide) (PPO-TPQP) was cast from three different solvents: dimethyl sulfoxide (DMSO), ethyl lactate, or a 41:59 vol% mixture of DMSO and ethyl lactate. Solvents were selected via analysis of the Hansen solubility parameters to vary the phase separation of the polymer in the films. An optimized mixture of DMSO and ethyl lactate chosen for film fabrication and this film was contrasted with films cast from the neat constituent solvents. Atomic force microscopy identified domains from nanometer to tens of nanometer sizes, while the light microscopy showed features on the order of micron. SAXSmore » revealed a cation scattering peak with a d-spacing from 7 to 15 A. Trends in conductivity and water diffusion for the membranes vary depending on the solvent from which they are cast. The mixed solvent cast membrane shows a linear Arrhenius behavior indicating fully dissociated cationic/anionic groups, and has the highest bromide conductivity of 3 mS/cm at 95% RH, 90 degrees C. The ethyl lactate cast membrane shows a linear Arrhenius relation in conductivity, but a Vogel-Tamman-Fulcher behavior in its water self-diffusion. While water increases bromide dissociation, water and bromide transport in these films seems to be decoupled. This is particularly true for the film cast from ethyl lactate.« less

Anion exchange membranes composed of a poly(2,6-dimethyl-1,4-phenylene oxide) random copolymer functionalized with a bulky phosphonium cation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Ye; Zhang, Bingzi; Kinsinger, Corey L.

A random copolymer, tris(2,4,6-trimethoxyphenyl) phosphonium functionalized poly(2,6-dimethyl-1,4-phenylene oxide) (PPO-TPQP) was cast from three different solvents: dimethyl sulfoxide (DMSO), ethyl lactate, or a 41:59 vol% mixture of DMSO and ethyl lactate. Solvents were selected via analysis of the Hansen solubility parameters to vary the phase separation of the polymer in the films. An optimized mixture of DMSO and ethyl lactate chosen for film fabrication and this film was contrasted with films cast from the neat constituent solvents. Atomic force microscopy identified domains from nanometer to tens of nanometer sizes, while the light microscopy showed features on the order of micron. SAXSmore » revealed a cation scattering peak with a d-spacing from 7 to 15 Å. Trends in conductivity and water diffusion for the membranes vary depending on the solvent from which they are cast. The mixed solvent cast membrane shows a linear Arrhenius behavior indicating fully dissociated cationic/anionic groups, and has the highest bromide conductivity of 3 mS/cm at 95% RH, 90 °C. The ethyl lactate cast membrane shows a linear Arrhenius relation in conductivity, but a Vogel-Tamman-Fulcher behavior in its water self-diffusion. While water increases bromide dissociation, water and bromide transport in these films seems to be decoupled. Lastly, this is particularly true for the film cast from ethyl lactate.« less

Imidazolium-Based Polymeric Materials as Alkaline Anion-Exchange Fuel Cell Membranes

NASA Technical Reports Server (NTRS)

Narayan, Sri R.; Yen, Shiao-Ping S.; Reddy, Prakash V.; Nair, Nanditha

2012-01-01

Polymer electrolyte membranes that conduct hydroxide ions have potential use in fuel cells. A variety of polystyrene-based quaternary ammonium hydroxides have been reported as anion exchange fuel cell membranes. However, the hydrolytic stability and conductivity of the commercially available membranes are not adequate to meet the requirements of fuel cell applications. When compared with commercially available membranes, polystyrene-imidazolium alkaline membrane electrolytes are more stable and more highly conducting. At the time of this reporting, this has been the first such usage for imidazolium-based polymeric materials for fuel cells. Imidazolium salts are known to be electrochemically stable over wide potential ranges. By controlling the relative ratio of imidazolium groups in polystyrene-imidazolium salts, their physiochemical properties could be modulated. Alkaline anion exchange membranes based on polystyrene-imidazolium hydroxide materials have been developed. The first step was to synthesize the poly(styrene-co-(1-((4-vinyl)methyl)-3- methylimidazolium) chloride through a free-radical polymerization. Casting of this material followed by in situ treatment of the membranes with sodium hydroxide solutions provided the corresponding hydroxide salts. Various ratios of the monomers 4-chloromoethylvinylbenzine (CMVB) and vinylbenzine (VB) provided various compositions of the polymer. The preferred material, due to the relative ease of casting the film, and its relatively low hygroscopic nature, was a 2:1 ratio of CMVB to VB. Testing confirmed that at room temperature, the new membranes outperformed commercially available membranes by a large margin. With fuel cells now in use at NASA and in transportation, and with defense potential, any improvement to fuel cell efficiency is a significant development.

A novel route to recognizing quaternary ammonium cations using electrospray mass spectrometry.

PubMed

Shackman, Holly M; Ding, Wei; Bolgar, Mark S

2015-01-01

Characterizing and elucidating structures is a commonplace and necessary activity in the pharmaceutical industry with mass spectrometry and NMR being the primary tools for analysis. Although many functional groups are readily identifiable, quaternary ammonium cations have proven to be difficult to unequivocally identify using these techniques. Due to the lack of an N-H bond, quaternary ammonium groups can only be detected in the (1)H NMR spectra by weak signals generated from long-range (14)N-H coupling, which by themselves are inconclusive evidence of a quaternary ammonium functional group. Due to their low intensity, these signals are frequently not detected. Additionally, ions cannot be differentiated in a mass spectrum as an M(+) or [M + H](+) ion without prior knowledge of the compound's structure. In order to utilize mass spectrometry as a tool for determining this functionality, ion cluster formation of quaternary ammonium cations and non-quaternary amines was studied using electrospray ionization. Several mobile phase modifiers were compared; however, the addition of small amounts of trifluoroacetic acid proved superior in producing characteristic and intense [M +2TFA](-) clusters for compounds containing quaternary ammonium cations when using negative electrospray. By fragmenting this characteristic ion using CID, nearly all compounds studied could be unambiguously identified as containing a quaternary ammonium cation or a non-quaternary amine attributable to the presence (non-quaternary amine) or absence (quaternary ammonium cation) of the resulting [2TFA + H](-) ion in the product spectra. This method of analysis provides a rapid, novel, and reliable technique for indicating the presence of quaternary ammonium cations in order to aid in structural elucidation.

Durable electrooptic devices comprising ionic liquids

DOEpatents

Burrell, Anthony K [Los Alamos, NM; Agrawal, Anoop [Tucson, AZ; Cronin,; John, P [Tucson, AZ; Tonazzi, Juan C. L. [Tucson, AZ; Warner, Benjamin P [Los Alamos, NM; McCleskey, T Mark [Los Alamos, NM

2009-12-15

Electrolyte solutions for electrochromic devices such as rear view mirrors and displays with low leakage currents are prepared using inexpensive, low conductivity conductors. Preferred electrolytes include bifunctional redox dyes and molten salt solvents with enhanced stability toward ultraviolet radiation. The solvents include lithium or quaternary ammonium cations, and perfluorinated sulfonylimide anions selected from trifluoromethylsulfonate (CF.sub.3SO.sub.3.sup.-), bis(trifluoromethylsulfonyl)imide ((CF.sub.3SO.sub.2).sub.2N.sup.-), bis(perfluoroethylsulfonyl)imide ((CF.sub.3CF.sub.2SO.sub.2).sub.2N.sup.-) and tris(trifluoromethylsulfonyl)methide ((CF.sub.3SO.sub.2).sub.3C.sup.-). Electroluminescent, electrochromic and photoelectrochromic devices with nanostructured electrodes include ionic liquids with bifunctional redox dyes. Some of the electrolyte solutions color to red when devices employing the solutions are powered, leading to red or neutral electrooptic devices.

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

NASA Astrophysics Data System (ADS)

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

2016-11-01

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

Durable Electrooptic Devices Comprising Ionic Liquids

DOEpatents

Burrell, Anthony K.; Agrawal, Anoop; Cronin, John P.; Tonazzi, Juan C. L.; Warner, Benjamin P.; McCleskey, T. Mark

2008-11-11

Electrolyte solutions for electrochromic devices such as rear view mirrors and displays with low leakage currents are prepared using inexpensive, low conductivity conductors. Preferred electrolytes include bifunctional redox dyes and molten salt solvents with enhanced stability toward ultraviolet radiation. The solvents include lithium or quaternary ammonium cations, and perfluorinated sulfonylimide anions selected from trifluoromethylsulfonate (CF.sub.3SO.sub.3.sup.-), bis(trifluoromethylsulfonyl)imide ((CF.sub.3SO.sub.2).sub.2N.sup.-), bis(perfluoroethylsulfonyl)imide ((CF.sub.3CF.sub.2SO.sub.2).sub.2N.sup.-) and tris(trifluoromethylsulfonyl)methide ((CF.sub.3SO.sub.2).sub.3C.sup.-). Electroluminescent, electrochromic and photoelectrochromic devices with nanostructured electrodes include ionic liquids with bifunctional redox dyes. Some of the electrolyte solutions color to red when devices employing the solutions are powered, leading to red or neutral electrooptic devices.

Resistance of Pseudomonas to Quaternary Ammonium Compounds. I. Growth in Benzalkonium Chloride Solution

PubMed Central

Adair, Frank W.; Geftic, Sam G.; Gelzer, Justus

1969-01-01

Resistant cells of Pseudomonas aeruginosa and a waterborne Pseudomonas sp. (strain Z-R) were able to multiply in nitrogen-free minimal salts solution containing various concentrations of commercially prepared, ammonium acetate-buffered benzalkonium chloride (CBC), a potent antimicrobial agent. As the CBC concentration increased, growth increased until a point was reached at which the extent of growth leveled off or was completely depressed. Minimal salts solutions of pure benzalkonium chloride (PBC) containing no ammonium acetate did not support bacterial growth. When ammonium acetate was added to PBC solutions in the same concentrations found in CBC solutions, growth patterns developed that were comparable to those found with CBC. Likewise, (NH4)2SO4 added to PBC solutions supported growth of both organisms. P. aeruginosa was initially resistant to CBC levels of 0.02% and it was adapted to tolerate levels as high as 0.36%. Strain Z-R was naturally resistant to 0.4% CBC. Since ammonium acetate, carried over by the CBC used in drug formulations and disinfectant solutions, has the potential to support the growth of resistant bacteria and thus make possible the risk of serious infection, it is suggested that regulations allowing the presence of ammonium acetate in CBC solution be reconsidered. PMID:4984761

Geology of the Gateway quadrangle, Mesa county Colorado

USGS Publications Warehouse

Cater, Fred W.

1953-01-01

The Gateway quadrangle is one of eighteen 7 1/2-minute quadrangles covering the principal carnotite-producing area of southwestern Colorado. The geology of these quadrangles was mapped by the U.S. Geological Survey for the Atomic Energy Commission as part of a comprehensive study of carnotite deposits. The rocks exposed in the eighteen quadrangles consist of crystalline rocks of pre-Cambrian age and sedimentary rocks that range in age from late Paleozoic to Quaternary. Over much of the area the sedimentary rocks are flat lying, but in places the rocks are disrupted by hih-angle faults, and northwest-trending folds. Conspicuous among the folds are large anticlines having cores of intrusive salt and gypsum. Most of the carnotite deposits are confined to the Salt Wash sandstone member of Jurassic Morrison formation. Within this sandstone, most of the deposits are spottily distributed through an arcuate zone known as "Uruvan Mineral Belt". Individual deposits range in size from irregular masses containing only a few tons of ore to large, tabular masses containing many thousands of tons. The ore consists largely of sandstone selectively impregnated and in part replaced by uranium and vanadium minerals. Most of the deposits appear to be related to certain sedimentary structures in sandstones of favorable composition.

Geology of the Egnar quadrangle, Dolores and San Miguel counties, Colorado

USGS Publications Warehouse

Cater, Fred W.; Bush, A.L.; Bell, Henry

1954-01-01

The Egnar quadrangle is one of eighteen 7 1/2-minute quadrangles covering the principal carnotite-producing area of southwestern Colorado. The geology of these quadrangles was mapped by the U.S. Geological Survey for the Atomic Energy Commission as part of a comprehensive study of carnotite deposits. The rocks exposed in the eighteen quadrangles consist of crystalline rocks of pre-Cambrian age and sedimentary rocks that range in age from late Paleozoic to Quaternary. Over much of the area the sedimentary rocks are flat lying, but in places the rocks are disrupted by hih-angle faults, and northwest-trending folds. Conspicuous among the folds are large anticlines having cores of intrusive salt and gypsum. Most of the carnotite deposits are confined to the Salt Wash sandstone member of Jurassic Morrison formation. Within this sandstone, most of the deposits are spottily distributed through an arcuate zone known as "Uruvan Mineral Belt". Individual deposits range in size from irregular masses containing only a few tons of ore to large, tabular masses containing many thousands of tons. The ore consists largely of sandstone selectively impregnated and in part replaced by uranium and vanadium minerals. Most of the deposits appear to be related to certain sedimentary structures in sandstones of favorable composition.

Geology of the Hamm Canyon quadrangle, Colorado

USGS Publications Warehouse

Cater, Fred W.

1953-01-01

The Hamm Canyon quadrangle is on eof eighteen 7 1/2-minute quadrangles covering the principal carnotite-producing area of southwestern Colorado. The geology of these quadrangles was mapped by the U.S. Geological Survey for the Atomic Energy Commission as part of a comprehensive study of carnotite deposits. The rocks exposed in the eighteen quadrangles consist of crystalline rocks of pre-Cambrian age and sedimentary rocks that range in age from late Paleozoic to Quaternary. Over much of the area the sedimentary rocks are flat lying, but in places the rocks are disrupted by high-angle faults, and northwest-trending folds. Conspicuous among the folds are large anticlines having cores of intrusive salt and gypsum. Most of the carnotite deposits are confined to the Salt Wash sandstone member of the Jurassic Morrison formation. Within this sandstone, most of the deposits are spottily distributed through an arcuate zone known as the "Uravan Mineral Belt". Individual deposits range in size from irregular masses containing only a few tons of ore to large, tabular masses containing many thousands of tons. The ore consists largely of sandstone selectively impregnated and in part replaced by uranium and vanadium minerals. Most of the deposits appear to be related to certain sedimentary structures in sandstones of favorable composition.

Geology of the Davis Mesa quadrangle, Colorado

USGS Publications Warehouse

Cater, Fred W.; Bryner, Leonid

1953-01-01

The Davis Mesa quadrangle is one of eighteen 7 1/2-minute quadrangles covering the principal carnotite-producing area of southwestern Colorado. The geology of these quadrangles was mapped by the U.S. Geological Survey for the Atomic Energy Commission as part of a comprehensive study of carnotite deposits. The rocks exposed in the eighteen quadrangles consist of crystalline rocks of pre-Cambrian age and sedimentary rocks that range in age from late Paleozoic to Quaternary. Over much of the area the sedimentary rocks are flat lying, but in places the rocks are disrupted by hih-angle faults, and northwest-trending folds. Conspicuous among the folds are large anticlines having cores of intrusive salt and gypsum. Most of the carnotite deposits are confined to the Salt Wash sandstone member of Jurassic Morrison formation. Within this sandstone, most of the deposits are spottily distributed through an arcuate zone known as "Uruvan Mineral Belt". Individual deposits range in size from irregular masses containing only a few tons of ore to large, tabular masses containing many thousands of tons. The ore consists largely of sandstone selectively impregnated and in part replaced by uranium and vanadium minerals. Most of the deposits appear to be related to certain sedimentary structures in sandstones of favorable composition.

Geology of the Joe Davis Hill quadrangle, Dolores and San Miguel counties, Colorado

USGS Publications Warehouse

Cater, Fred W.; Bell, Henry

1953-01-01

The Joe Davis Hill quadrangle is one of eighteen 7 1/2-minute quadrangles covering the principal carnotite-producing area of southwestern Colorado. The geology of these quadrangles was mapped by the U.S. Geological Survey for the Atomic Energy Commission as part of a comprehensive study of carnotite deposits. The rocks exposed in the eighteen quadrangles consist of crystalline rocks of pre-Cambrian age and sedimentary rocks that range in age from late Paleozoic to Quaternary. Over much of the area the sedimentary rocks are flat lying, but in places the rocks are disrupted by hih-angle faults, and northwest-trending folds. Conspicuous among the folds are large anticlines having cores of intrusive salt and gypsum. Most of the carnotite deposits are confined to Salt Wash sandstone member of the Jurassic Morrison formation. Within this sandstone, most of the deposits are spottily distributed through an arcuate zone known as the "Uravan Mineral Belt". Individual deposits range in size from irregular masses containing only a few tons of ore to large, tabular masses containing many thousands of tons. The ore consists largely of sandstone selectively impregnated and in part replaced by uranium and vanadium minerals. Most of the deposits appear to be related to certain sedimentary structures in sandstones of favorable composition.

Geology of the Gypsum Gap quadrangle, Colorado

USGS Publications Warehouse

Cater, Fred W.

1953-01-01

The Gypsum Gap quadrangle is one eighteen 7 1/2-minute quadrangles covering the principal carnotite-producing area of southwestern Colorado. The geology of these quadrangles was mapped by the U.S. Geological Survey for the Atomic Energy Commission as part of a comparative study of carnotite deposits. The rocks exposed in the eighteen quadrangles consist of crystalline rocks of pre-Cambrian age and sedimentary rocks that range in age from late Paleozoic to Quaternary. Over much of the area the sedimentary rocks are flat lying, but in places the rocks are disrupted by high-angle faults, and northwest-trending folds. Conspicuous among the folds are large anticlines having cores of intrusive salt and gypsum. Most of the carnotite deposits are confined to the Salt Wash sandstone member of the Jurassic Morrison formation. Within this sandstone, most of the deposits are spottily distributed through a arcuate zone known as the "Uravan Mineral Belt". Individual deposits range in size from irregular masses containing only a few tons of ore to large, tabular masses containing many thousands of tons. The core consists largely of sandstone selectively impregnated and in part replaced by uranium and vanadium minerals. Most of the deposits appear to be related to certain sedimentary structures in sandstones of favorable composition.

Geology of the Pine Mountain quadrangle, Mesa county, Colorado

USGS Publications Warehouse

Cater, Fred W.

1953-01-01

The Pine Mountain quadrangle is one of eighteen 7 1/2-minute quadrangles covering the principal carnotite-producing area of southwestern Colorado. The geology of these quadrangles was mapped by the U.S. Geological Survey for the Atomic Energy Commission as part of a comprehensive study of carnotite deposits. The rocks exposed in the eighteen quadrangles consist of crystalline rocks of pre-Cambrian age and sedimentary rocks that range in age from Paleozoic to Quaternary. Over mush of the area the sedimentary rocks are flat lying, but in places the rocks are disrupted by high-angle faults, and northwest-trending folds. Conspicuous among the folds are large anticlines having cores of intrusive salt and gypsum. Most of the carnotite deposits are confines to the Salt Wash sandstone member of the Jurassic Morrison formation. Within this sandstone, most of the deposits are spottily distributed through an arcuate zone known as the "Uravan Mineral Belt". Individual deposits range in sizer from irregular masses containing only a few ton of ore to large, tabular masses containing many thousands of tons. The ore consists largely of sandstone selectively impregnated and in part replaced by uranium and vanadium minerals. Most of the deposits appear to be related to certain sedimentary structures in sandstones of favorable composition.

Geology of the Naturita NW quadrangle, Colorado

USGS Publications Warehouse

Cater, Fred W.; Vogel, J.D.

1953-01-01

The Naturita NW quadrangle is one of eighteen 7 1/2-minute quadrangles covering the principal carnotite-producing area of southwestern Colorado. The geology of these quadrangles were mapped by the U.S. Geological Survey on behalf of the U.S. Atomic Energy Commission as part of a comprehensive study of carnotite deposits. The rocks exposed in the eighteen quadrangles consist of crystalline rocks of pre-Cambrian age and sedimentary rocks that range in age from late Paleozoic to Quaternary. Over much of the area the sedimentary rocks are flat lying, but in places the rocks are disrupted by high-angle faults, and northwest-trending folds. Conspicuous among the folds are large anticlines having cores of intrusive salt and gypsum. Most of the carnotite deposits are confined to the Salt Wash sandstone member of the Jurassic Morrison formation. Within this sandstone, most of the deposits are spottily distributed through an arcuate zone known as the "Uravan Mineral Belt". Individual deposits range in size from irregular masses containing only a few tons of ore to large, tabular masses containing many thousands of tons. The ore consists largely of sandstone selectively impregnated and in part replaced by uranium and vanadium minerals. Most of the deposits appear ro be related to certain sedimentary structures in sandstones of favorable composition.

Geology of the Calamity Mesa quadrangle, Mesa county, Colorado

USGS Publications Warehouse

Cater, Fred W.; Stager, Harold K.

1953-01-01

The Calamity Mesa quadrangle is one of eighteen 7 1/2-minute quadrangles covering the principal carnotite-producing area of southwestern Colorado. The geology of these quadrangles was mapped by the U.S. Geological Survey for the Atomic Energy Commission as part of a comprehensive study of carnotite deposits. The rocks exposed in the eighteen quadrangles consist of crystalline rocks of pre-Cambrian age and sedimentary rocks the range in age from late Paleozoic to Quaternary. Over much of the area the sedimentary rocks are flat lying, but in places the rocks are disrupted by high-angle faults, and northwest-trending folds. Conspicuous among the folds are large anticlines having cores of intrusive salt and gypsum. Most of the carnotite deposits are confined to the Salt Wash sandstone member of the Jurassic Morrison formation. Within this sandstone, most of the deposits are spottily distributed through an arcuate zone known as the "Uravan Mineral Belt". Individual deposits range in size from irregular masses containing only a few tons of ore to large tabular masses containing many thousands of tons. The ore consists largely of sandstone selectively impregnated and in part replaced by uranium and vanadium minerals. Most of the deposits appear to be related to certain sedimentary structures in sandstones of favorable composition.

Geology of the Horse Range Mesa quadrangle, Colorado

USGS Publications Warehouse

Cater, Fred W.; Bush, A.L.; Bell, Henry; Withington, C.F.

1953-01-01

The Horse Range Mesa quadrangle is one of eighteen 7 1/2-minute quadrangles covering the principal carnotite-producing area of southwestern Colorado. The geology of the quadrangles was mapped by the U.S. Geological Survey for the Atomic Energy Commission as part of a comprehensive study of carnotite deposits. The rocks exposed in the eighteen quadrangles consist of crystalline rocks of pre-Cambrian age and sedimentary rocks that range in age from late Paleozoic to Quaternary. Over much of the area the sedimentary rocks are flat lying, but in places the rocks are disrupted by high-angle faults, and northwest-trending folds. Conspicuous among the folds are large anticlines having cores of intrusive salt and gypsum. Most of the carnotite deposits are confined to the Salt Wash sandstone member of the Jurassic Morrison formation. Within this sandstone, most of the deposits are spottily distributed through an arcuate zone known as the "Uravan Mineral Belt". Individual deposits range in size from irregular masses containing only a few tons of ore to large, tabular masses containing many thousands of tons. The ore consists largely of sandstone selectively impregnated and in part replaced by uranium and vanadium minerals. Most of the deposits appear to be related to certain sedimentary strictures in sandstones of favorable composition.

Geology of Bull Canyon quadrangle, Montrose and San Miguel counties, Colorado

USGS Publications Warehouse

Cater, Fred W.

1953-01-01

The Bull Canyon quadrangle is one of eighteen 7 1/2-minute quadrangles covering the principal carnotite-producing area of southwestern Colorado. The geology of these quadrangles was mapped by the U.S. Geological Survey for the Atomic Energy Commission as part of a comprehensive study of carnotite depots. The rocks exposed in the eighteen quadrangles consist of crystalline rocks of pre-Cambrian age and sedimentary rocks that range in age from late Paleozoic to Quaternary. Over much of the area the sedimentary rocks are flat lying, but in places the rocks are disrupted by high-angle faults and northwest-trending folds. Conspicuous among the folds are large anticlines having cores of intrusive salt and gypsum. Most of the carnotite deposits are confined to the Salt Wash sandstone member of the Jurassic Morrison formation. Within this sandstone, most of the deposits are spottily distributed through an arcuate zone known as the "Uravan Mineral Belt". Individual deposits range in size from irregular masses containing only a few tons of ore to large, tabular masses containing many thousands of tones. The ore consists largely of sandstone selectively impregnated and in part replaced by uranium and vanadium minerals. Most of the deposits appear to be related to certain sedimentary structures in sandstones of favorable composition.

Geology of the Uravan quadrangle, Montrose county, Colorado

USGS Publications Warehouse

Cater, Fred W.; Butler, A.P.; McKay, E.J.; Boardman, Robert L.

1954-01-01

The Uravan quadrangle is one of eighteen 7 1/2-minute quadrangles covering the principal carnotite-producing area of the southwestern Colorado. The geology of these quadrangles was mapped by the U.S. Geological Survey for the Atomic Energy Commission as part of a comprehensive study of carnotite deposits. The rocks exposed in the eighteen quadrangles consist of crystalline rocks of pre-Cambrian age and sedimentary rocks that range in age from late Paleozoic to Quaternary. Over much of the area the sedimentary rocks are flat lying, but in places the rocks are disrupted by high-angle faults, and northwest-trending folds. Conspicuous among the folds are large anticlines having cores of intrusive salt and gypsum. Most of the carnotite deposits are confined to the Salt Wash sandstone member of the Jurassic Morrison formation. Within this sandstone, most of the deposits are spottily distributed through an arcuate zone known as the "Uravan Mineral Belt". Individual deposits range in size from irregular masses containing only a few tons of ore to large, tabular masses containing many thousands of tons. The ore consists largely of sandstone selectively impregnated and in part replaced by uranium and vanadium minerals. Most of the deposits appear to the related to certain sedimentary structures in sandstones of favorable composition.

Novel oxotremorine-related heterocyclic derivatives: Synthesis and in vitro pharmacology at the muscarinic receptor subtypes.

PubMed

Dallanoce, Clelia; De Amici, Marco; Barocelli, Elisabetta; Bertoni, Simona; Roth, Bryan L; Ernsberger, Paul; De Micheli, Carlo

2007-12-15

A set of novel heterocyclic ligands (6-27) structurally related to Oxotremorine 2 was designed, synthesized and tested at muscarinic receptor subtypes (mAChRs). In the binding experiments at cloned human receptors (hm1-5), compounds 7 and 15 evidenced a remarkable affinity and selectivity for the hm2 subtype. The in vitro functional assays, performed on a selected group of derivatives at M(1), M(2), and M(3) tissue preparations, singled out the 3-butynyloxy-5-methylisoxazole trimethylammonium salt 7 as a potent unselective muscarinic agonist [pEC(50): 7.40 (M(1)), 8.18 (M(2)), and 8.14 (M(3))], whereas its 5-phenyl analogue 12 behaved as a muscarinic antagonist, slightly selective for the M(1) subtype [pK(B): 6.88 (M(1)), 5.95 (M(2)), 5.53 (M(3))]. Moreover, the functional data put in evidence that the presence of the piperidine ring may generate a functional selectivity, e.g., an M(1) antagonist/M(2) partial agonist/M(3) full agonist profile (compound 21), at variance with the corresponding quaternary ammonium salt (compound 22) which behaved as a muscarinic agonist at all M(1-3) receptors, with an appreciable selectivity for the cardiac M(2) receptors.

Partitioning of deformation along a reactivated rifted margin: example of the northern Ligurian margin.

NASA Astrophysics Data System (ADS)

Sage, Françoise; Beslier, Marie-Odile; Gaullier, Virginie; Larroque, Christophe; Dessa, Jean-Xavier; Mercier de Lepinay, Bernard; Corradi, Nicola; Migeon, Sébastien; Katz, Hélène; Ruiz Constan, Ana

2013-04-01

The northern Ligurian margin, of Oligo-Miocene age, is currently undergoing compression related to microplate motions and/or to gravity spreading of the Alpine chain located immediately north of it. Active thrust faults and folds have previously been identified below the margin, together with a global uplift of the continental edge, since at least the Messinian. The seismicity that goes with the present-day margin contraction (e.g. Mw 6.9, 1887/02/23) extends to the axis of the adjacent oceanic basin (e.g. ML 6.0, 1963/07/19; ML 5.4, 2011/07/07). However, we do not know of any recent or active crustal contractional structure within this oceanic domain. In this study, we use new 12-channel high-resolution seismic data (FABLES seismic cruise, 2012, R/V Tethys II) in order to image the sedimentary cover of the Ligurian oceanic basin, up to ~3km below the seabed, including the Plio-Quaternary and the Messinian sediment down to the bottom of the Messinian salt layer. Because the Messinian event is well dated (5.96-5.32 Ma) and well identified in the seismic data, it forms a clear marker that we use to characterize the recent deformation related to both mobile salt motion and crustal tectonics. About 50 km south of the margin offshore of Italy, we identify huge and complex salt walls that elongate SW-NE. Such salt walls, which cannot be explained by salt tectonics only, are interpreted as evidence of deep-seated crustal deformation. They form en echelon structures that are well expressed in the seabed morphology, and do not correspond to any significant vertical throw at the base of the salt layer. This suggests that within the deep basin, mainly strike-slip faulting accommodates long-term crustal deformation. It thus offers a contrast with the margin where deformation is mainly marked by shortening and reverse faulting, with vertical throws of several hundred meters. This discrepancy in the tectonic styles between the margin and the adjacent oceanic basin suggests some partitioning of the deformation. It may result from the difference in the topographic gradient of the main crustal interfaces between the steep margin and the adjacent oceanic domain, and/or to different mechanical behaviours of the adjacent lithospheric domains.

Quaternary and Geomorphology.

ERIC Educational Resources Information Center

Andrews, J. T.; Graf, W. L.

1983-01-01

Highlights conferences and meetings of organizations involved with quaternary geology and geomorphology, including International Union of Quaternary Research Conference held in Moscow. The impetus of a revision of "The Quaternary of the United States" resulted from this conference. Includes activities/aims of "Friends of the…

3D coupled heat and mass transfer processes at the scale of sedimentary basisn

NASA Astrophysics Data System (ADS)

Cacace, M.; Scheck-Wenderoth, M.; Kaiser, B. O.

2014-12-01

We use coupled 3D simulations of fluid, heat, and transport based on a 3D structural model of a complex geological setting, the Northeast German Basin (NEGB). The geological structure of the NEGB is characterized by a relatively thick layer of Permian Zechstein salt, structured in differnet diapirs (up to 5000 m thick) and pillows locally reaching nearly the surface. Salt is thermally more conductive than other sediments, hydraulically impervious but highly solvable. Thus salt structures have first order influence on the temperature distribution, the deep flow regime and the salinity of groundawater bearing aquifers. In addition, the post-Permian sedimentary sequence is vertically subdivided into several aquifers and aquitards. The shallow Quaternary to late Tertiary freshwater aquifer is separated from the underlying Mesozoic saline aquifers by an embedded Tertiary clay enriched aquitard (Rupelian Aquitard). An important feature of this aquitard is that hydraulic connections between the upper and lower aquifers exist in areas where the Rupelian Aquitard is missing (hydrogeological windows). By means of 3D numerical simulations we explore the role of heat conduction, pressure, and density driven groundwater flow as well as fluid viscosity-related and salinity-dependent effects on the resulting flow and temperature fields. Our results suggest that the regional temperature distribution within the basin results from interactions between regional pressure forces and thermal diffusion locally enhanced by thermal conductivity contrasts between the different sedimentary rocks with the highly conductive salt. Buoyancy forces triggered by temperature-dependent fluid density variations affect only locally the internal thermal configuration. Locations, geometry, and wavelengths of convective thermal anomalies are mainly controlled by the permeability field and thickness values of the respective geological layers. Numerical results from 3D thermo-haline numerical simulations suggest that hydrogeological windows act as preferential domains of hydraulic interconnectivity between the different aquifers at depth, and enable vigorous heat and mass transport which causes a mixing of warm and saline groundwater with cold and less saline groundwater within both aquifers.

Bathymetry of the Levant basin: interaction of salt-tectonics and surficial mass movements

NASA Astrophysics Data System (ADS)

Gvirtzman, Zohar; Reshef, Moshe; Buch-Leviatan, Orna; Groves-Gidney, Gavrielle; Karcz, Zvi; Makovsky, Yizhaq; Ben-Avraham, Zvi

2015-04-01

A new high resolution bathymetric map of the Levant Basin between Israel and the Eratosthenes Seamount reveals previously undetected folds, faults and channels. The map facilitates a regional map-view analysis of structures that were previously examined only in cross section. The systematic mapping of morpho-structural elements in the entire basin is followed by a kinematic interpretation that distinguished between two main processes sculpting the seabed from bottom and top: salt tectonics and sediment transport. We show that the contractional domain related to salt tectonics is far more complex than previously thought. Ridges, previously interpreted as contractional folds are, in fact, surficial undulations of the seabed reminiscent of sediment waves. Moreover, other folds previously interpreted as downdip contraction of the westward gliding Plio-Quaternary section are, in some parts of the basin, caused by updip climbing of this section eastwards as a result of the regional pattern of salt flow away from the Nile Cone. In the context of sediment transport, we show that the northern Sinai continental slope is covered by a dense net of turbidite channels, whereas the Levant slope has no channels at all. Particularly interesting is the Levant Turbidite Channel, described and named here for the first time. This feature begins at the southeastern corner of the Mediterranean at water depths of ~1100 m, continues along the valley between the Sinai and Levant slopes, and reaches the deepest part of the basin, in water depths of ~2500 m, northeast of the Eratosthenes seamount. However, this prominent feature cannot be explained by the current drainage, consisting of two minor rivers that enter the basin at that point, and thus most likely reflects periods of wetter climate and/or lower sea-level, when these rivers were more active and possibly connected to the submarine channel system.

Exceptionally well preserved late Quaternary plant and vertebrate fossils from a blue hole on Abaco, The Bahamas.

PubMed

Steadman, David W; Franz, Richard; Morgan, Gary S; Albury, Nancy A; Kakuk, Brian; Broad, Kenneth; Franz, Shelley E; Tinker, Keith; Pateman, Michael P; Lott, Terry A; Jarzen, David M; Dilcher, David L

2007-12-11

We report Quaternary vertebrate and plant fossils from Sawmill Sink, a "blue hole" (a water-filled sinkhole) on Great Abaco Island, The Bahamas. The fossils are well preserved because of deposition in anoxic salt water. Vertebrate fossils from peat on the talus cone are radiocarbon-dated from approximately 4,200 to 1,000 cal BP (Late Holocene). The peat produced skeletons of two extinct species (tortoise Chelonoidis undescribed sp. and Caracara Caracara creightoni) and two extant species no longer in The Bahamas (Cuban crocodile, Crocodylus rhombifer; and Cooper's or Gundlach's Hawk, Accipiter cooperii or Accipiter gundlachii). A different, inorganic bone deposit on a limestone ledge in Sawmill Sink is a Late Pleistocene owl roost that features lizards (one species), snakes (three species), birds (25 species), and bats (four species). The owl roost fauna includes Rallus undescribed sp. (extinct; the first Bahamian flightless rail) and four other locally extinct species of birds (Cooper's/Gundlach's Hawk, A. cooperii/gundlachii; flicker Colaptes sp.; Cave Swallow, Petrochelidon fulva; and Eastern Meadowlark, Sturnella magna) and mammals (Bahamian hutia, Geocapromys ingrahami; and a bat, Myotis sp.). The exquisitely preserved fossils from Sawmill Sink suggest a grassy pineland as the dominant plant community on Abaco in the Late Pleistocene, with a heavier component of coppice (tropical dry evergreen forest) in the Late Holocene. Important in its own right, this information also will help biologists and government planners to develop conservation programs in The Bahamas that consider long-term ecological and cultural processes.

Relationships between lake-level changes and water and salt budgets in the Dead Sea during extreme aridities in the Eastern Mediterranean

NASA Astrophysics Data System (ADS)

Kiro, Yael; Goldstein, Steven L.; Garcia-Veigas, Javier; Levy, Elan; Kushnir, Yochanan; Stein, Mordechai; Lazar, Boaz

2017-04-01

Thick halite intervals recovered by the Dead Sea Deep Drilling Project cores show evidence for severely arid climatic conditions in the eastern Mediterranean during the last three interglacials. In particular, the core interval corresponding to the peak of the last interglacial (Marine Isotope Stage 5e or MIS 5e) contains ∼30 m of salt over 85 m of core length, making this the driest known period in that region during the late Quaternary. This study reconstructs Dead Sea lake levels during the salt deposition intervals, based on water and salt budgets derived from the Dead Sea brine composition and the amount of salt in the core. Modern water and salt budgets indicate that halite precipitates only during declining lake levels, while the amount of dissolved Na+ and Cl- accumulates during wetter intervals. Based on the compositions of Dead Sea brines from pore waters and halite fluid inclusions, we estimate that ∼12-16 cm of halite precipitated per meter of lake-level drop. During periods of halite precipitation, the Mg2+ concentration increases and the Na+/Cl- ratio decreases in the lake. Our calculations indicate major lake-level drops of ∼170 m from lake levels of 320 and 310 m below sea level (mbsl) down to lake levels of ∼490 and ∼480 mbsl, during MIS 5e and the Holocene, respectively. These lake levels are much lower than typical interglacial lake levels of around 400 mbsl. These lake-level drops occurred as a result of major decreases in average fresh water runoff, to ∼40% of the modern value (pre-1964, before major fresh water diversions), reflecting severe droughts during which annual precipitation in Jerusalem was lower than 350 mm/y, compared to ∼600 mm/y today. Nevertheless, even during salt intervals, the changes in halite facies and the occurrence of alternating periods of halite and detritus in the Dead Sea core stratigraphy reflect fluctuations between drier and wetter conditions around our estimated average. The halite intervals include periods that are richer and poorer in halite, indicating (based on the sedimentation rate) that severe dry conditions with water availability as low as ∼20% of the present day, continued for periods of decades to centuries, and fluctuated with wetter conditions that spanned centuries to millennia when water availability was ∼50-100% of the present day. These conclusions have potential implications for the coming decades, as climate models predict greater aridity in the region.

21 CFR 172.165 - Quaternary ammonium chloride combination.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Quaternary ammonium chloride combination. 172.165... HUMAN CONSUMPTION Food Preservatives § 172.165 Quaternary ammonium chloride combination. The food additive, quaternary ammonium chloride combination, may be safely used in food in accordance with the...

Quaternary prevention: reviewing the concept.

PubMed

Martins, Carlos; Godycki-Cwirko, Maciek; Heleno, Bruno; Brodersen, John

2018-12-01

According to the Wonca International Dictionary for General/Family Practice Quaternary Prevention is defined as: 'Action taken to identify patient at risk of overmedicalization, to protect him from new medical invasion, and to suggest to him interventions, which are ethically acceptable.' The concept of quaternary prevention was initially proposed by Marc Jamoulle and the targets were mainly patients with illness but without a disease. The purpose of this opinion article is to open the debate around a new possible definition and a new conceptual model of quaternary prevention based on the belief that quaternary prevention should be present in physicians' minds for every intervention they suggest to a patient. The debate around quaternary prevention is vital in the context of contemporary medicine and has expanded worldwide. The human being may suffer harm from medical interventions from conception, during their childhood, during their entire healthy lifetime as well as during a self-limited disease, a chronic disease, or a terminal disease. The current definition of quaternary prevention has limitations because it excludes patients and medical interventions where a quaternary prevention perspective would be needed and useful to protect patients from harm. In this context, a new definition and conceptual model of quaternary prevention is proposed. In this new proposal, quaternary prevention is defined as an 'action taken to protect individuals (persons/patients) from medical interventions that are likely to cause more harm than good.'

Using the salt tectonics as a proxy to reveal post-rift active crustal tectonics: The example of the Eastern Sardinian margin

NASA Astrophysics Data System (ADS)

Lymer, Gaël; Vendeville, Bruno; Gaullier, Virginie; Chanier, Frank; Gaillard, Morgane

2017-04-01

The Western Tyrrhenian Basin, Mediterranean Sea, is a fascinating basin in terms of interactions between crustal tectonics, salt tectonics and sedimentation. The METYSS (Messinian Event in the Tyrrhenian from Seismic Study) project is based on 2100 km of HR seismic data acquired in 2009 and 2011 along the Eastern Sardinian margin. The main aim is to study the Messinian Salinity Crisis (MSC) in the Western Tyrrhenian Basin, but we also investigate the thinning processes of the continental crust and the timing of crustal vertical motions across this complex domain. Our first results allowed us to map the MSC seismic markers and to better constrain the timing of the rifting, which ended before the MSC across the upper and middle parts of the margin. We also evidenced that crustal activity persisted long after the end of rifting. This has been particularly observed on the upper margin, where several normal faults and a surprising compressional structure were recently active. In this study we investigate the middle margin, the Cornaglia Terrace, where the Mobile Unit (MU, mobile Messinian salt) accumulated during the MSC and acts as a décollement. Our goal is to ascertain whether or not crustal tectonics existed after the pre-MSC rift. This is a challenge where the MU is thick, because potential basement deformations could be first accommodated by the MU and therefore would not find any expression in the supra-salt layers (Upper Unit, UU and Plio-Quaternary, PQ). However our investigations clearly reveal interactions between crustal and salt tectonics along the margin. We thus evidence gravity gliding of the salt and its brittle sedimentary cover along basement slopes generated by the post-MSC tilting of some basement blocks bounded by crustal normal faults, formerly due to the rifting. Another intriguing structure also got our interest. It corresponds to a wedge-shaped of MU located in a narrow N-S half graben bounded to the west by a major, east-verging, crustal normal fault. Below the MU, the sediments thicken toward the fault. The top of the MU is sub-horizontal and the supra-salt layers are sub-horizontal. At a first glance this geometry would suggest that the pre-salt unit and the MU are syn-tectonic and that nothing happened after Messinian times. However some subtle evidence of deformations in the UU and PQ (an anticline to the west and a small west-verging normal fault in the east) imply that some crustal tectonics activity persisted after the end of the rifting. To understand why the salt unit is wedge-shaped, we considered several scenarii that we tested with physical modelling. We demonstrate that this structure is related to the post-rift activity of the major crustal normal fault, whose vertical motion has been cushioned by lateral flow of an initially tabular salt layer, which thinned upslope and inflated downslope, keeping the overlying sediments remained sub-horizontal. Such interactions between thin-skinned and thick-skinned tectonics highlight how the analysis of the salt tectonics is a powerful tool to reveal recent deep crustal tectonics in the Western Mediterranean Basin.

Designing Novel Quaternary Quantum Reversible Subtractor Circuits

NASA Astrophysics Data System (ADS)

Haghparast, Majid; Monfared, Asma Taheri

2018-01-01

Reversible logic synthesis is an important area of current research because of its ability to reduce energy dissipation. In recent years, multiple valued logic has received great attention due to its ability to reduce the width of the reversible circuit which is a main requirement in quantum technology. Subtractor circuits are between major components used in quantum computers. In this paper, we will discuss the design of a quaternary quantum reversible half subtractor circuit using quaternary 1-qudit, 2-qudit Muthukrishnan-Stroud and 3-qudit controlled gates and a 2-qudit Generalized quaternary gate. Then a design of a quaternary quantum reversible full subtractor circuit based on the quaternary half subtractor will be presenting. The designs shall then be evaluated in terms of quantum cost, constant input, garbage output, and hardware complexity. The proposed quaternary quantum reversible circuits are the first attempt in the designing of the aforementioned subtractor.

High-Temperature Shape Memory Polymers

NASA Technical Reports Server (NTRS)

Yoonessi, Mitra; Weiss, Robert A.

2012-01-01

physical conformation changes when exposed to an external stimulus, such as a change in temperature. Such materials have a permanent shape, but can be reshaped above a critical temperature and fixed into a temporary shape when cooled under stress to below the critical temperature. When reheated above the critical temperature (Tc, also sometimes called the triggering or switching temperature), the materials revert to the permanent shape. The current innovation involves a chemically treated (sulfonated, carboxylated, phosphonated, or other polar function group), high-temperature, semicrystalline thermoplastic poly(ether ether ketone) (Tg .140 C, Tm = 340 C) mix containing organometallic complexes (Zn++, Li+, or other metal, ammonium, or phosphonium salts), or high-temperature ionic liquids (e.g. hexafluorosilicate salt with 1-propyl-3- methyl imidazolium, Tm = 210 C) to form a network where dipolar or ionic interactions between the polymer and the low-molecular-weight or inorganic compound forms a complex that provides a physical crosslink. Hereafter, these compounds will be referred to as "additives". The polymer is semicrystalline, and the high-melt-point crystals provide a temporary crosslink that acts as a permanent crosslink just so long as the melting temperature is not exceeded. In this example case, the melting point is .340 C, and the shape memory critical temperature is between 150 and 250 C. PEEK is an engineering thermoplastic with a high Young fs modulus, nominally 3.6 GPa. An important aspect of the invention is the control of the PEEK functionalization (in this example, the sulfonation degree), and the thermal properties (i.e. melting point) of the additive, which determines the switching temperature. Because the compound is thermoplastic, it can be formed into the "permanent" shape by conventional plastics processing operations. In addition, the compound may be covalently cross - linked after forming the permanent shape by S-PEEK by applying ionizing radiation ( radiation, neutrons), or by chemical crosslinking to form a covalent permanent network. With respect to other shape memory polymers, this invention is novel in that it describes the use of a thermoplastic composition that can be thermally molded or solution-cast into complex "permanent" shapes, and then reheated or redissolved and recast from solution to prepare another shape. It is also unique in that the shape memory behavior is provided by a non-polymer additive.

Triply Periodic Multiply Continuous Lyotropic Liquid Crystals Derived from Gemini Surfactants

NASA Astrophysics Data System (ADS)

Sorenson, Gregory P.

A subtle balance of non-covalent interactions directs the self-assembly of small molecule amphiphiles in aqueous media into supramolecular assemblies known as aqueous lyotropic liquid crystals (LLCs). Aqueous LLCs form many intricate, ordered nanoscale morphologies comprising distinct and structurally periodic hydrophobic and hydrophilic domains. Triply periodic multiply continuous (TPMC) LLC morphologies, which exhibit continuous hydrophobic and aqueous domains that percolate in three-dimensions, are of particular interest by virtue of their potentially wide ranging technological applications including advanced membranes for electrical energy storage and utilization, therapeutic delivery, and templates for new organic and inorganic mesoporous materials. However, robust molecular design criteria for amphiphiles that readily form TMPC morphologies are notably lacking in the literature. Recent reports have described the increased propensity for quaternary ammonium and phosphonium gemini surfactants, derived from dimerization of traditional single-tail surfactants at or near the hydrophilic headgroups through a hydrophobic linker, to stabilize TMPC mesophases. The generality of this surfactant design strategy remains untested in other amphiphiles classes bearing different headgroup chemistries. In this thesis, we describe the unusual aqueous LLC phase behavior of series of gemini dicarboxylate amphiphiles as a function of the alkyl tail length, hydrophobic linker length, and the charge-compensating counterion. These dicarboxylate surfactants unexpectedly exhibit a strong propensity to form TPMC LLCs over amphiphile concentration windows as wide as 20 wt% over a temperature range T = 25--100 °C. Through systematic modifications of the length of the hydrophobic linker and alkyl tails, we use small-angle X-ray scattering to demonstrate that these surfactants adopt new LLC mesophases including the first report of a single-gyroid phase (I4132 symmetry) and a new, tetracontinuous hexagonal network phase ( P63/mcm symmetry). Additionally, we probe the role of the linker position in the surfactant architecture. These data taken together indicate the sensitive dependence of the LLC phase behavior on counterion-headgroup correlations. Based on these molecular design criteria, we demonstrate the synthesis of a polymerizable gemini surfactant that may be self-assembled into a TPMC LLC phase and covalently fixed by a crosslinking photopolymerization. Comprised of aqueous nanochannels lined with metal carboxylates, the resulting LLC membranes exhibit high ionic conductivities.

Linker design for the modular assembly of multifunctional and targeted platinum(ii)-containing anticancer agents.

PubMed

Ding, S; Bierbach, U

2016-08-16

A versatile and efficient modular synthetic platform was developed for assembling multifunctional conjugates and targeted forms of platinum-(benz)acridines, a class of highly cytotoxic DNA-targeted hybrid agents. The synthetic strategy involved amide coupling between succinyl ester-modified platinum compounds (P1, P2) and a set of 11 biologically relevant primary and secondary amines (N1-N11). To demonstrate the feasibility and versatility of the approach, a structurally and functionally diverse range of amines was introduced. These include biologically active molecules, such as rucaparib (a PARP inhibitor), E/Z-endoxifen (an estrogen receptor antagonist), and a quinazoline-based tyrosine kinase inhibitor. Micro-scale reactions in Eppendorf tubes or on 96-well plates were used to screen for optimal coupling conditions in DMF solution with carbodiimide-, uronium-, and phosphonium-based compounds, as well as other common coupling reagents. Reactions with the phosphonium-based coupling reagent PyBOP produced the highest yields and gave the cleanest conversions. Furthermore, it was demonstrated that the chemistry can also be performed in aqueous media and is amenable to parallel synthesis based on multiple consecutive reactions in DMF in a "one-tube" format. In-line LC-MS was used to assess the stability of the conjugates in physiologically relevant buffers. Hydrolysis of the conjugates occurs at the ester moiety and is facilitated by the aquated metal moiety under low-chloride ion conditions. The rate of ester cleavage greatly depends on the nature of the amine component. Potential applications of the linker technology are discussed.

Ionic Liquid Films at the Water-Air Interface: Langmuir Isotherms of Tetra-alkylphosphonium-Based Ionic Liquids.

PubMed

Shimizu, Karina; Canongia Lopes, José N; Gonçalves da Silva, Amélia M P S

2015-08-04

The behavior of ionic liquids trihexyl(tetradecyl)phosphonium bis(trifluoromethylsulfonyl)imide and trihexyl(tetradecyl)phosphonium dicyanamide, [P6 6 6 14][Ntf2] and [P6 6 6 14][N(CN)2], respectively, at the water-air interface was investigated using the Langmuir trough technique. The obtained surface pressure versus mean molecular area (MMA) isotherms, π-A, and surface potential versus MMA isotherms, ΔV-A, show distinct interfacial behavior between the two systems. The results were interpreted at a molecular level using molecular dynamics simulations: the different compression regimes along the [P6 6 6 14][Ntf2] isotherm correspond to the self-organization of the ions at the water surface into compact and planar monolayers that coalesce at an MMA value of ca. 1.85 nm(2)/ion pair to form an expanded liquidlike layer. Upon further compression, the monolayer collapses at around 1.2 nm(2)/ion pair to yield a progressively thicker and less organized layer. These transitions are much more subdued in the [P6 6 6 14][N(CN)2] system because of the more hydrophilic nature of the dicyanamide anion. The numerical density profiles obtained from the MD simulation trajectories are also able to emphasize the very unusual packing of the four long alkyl side chains of the cation above and below the ionic layer that forms at the water surface. Such a distribution is also different for the two studied systems during the different compression regimes.

Quaternary prevention: reviewing the concept

PubMed Central

Martins, Carlos; Godycki-Cwirko, Maciek; Heleno, Bruno; Brodersen, John

2018-01-01

Abstract Background: According to the Wonca International Dictionary for General/Family Practice Quaternary Prevention is defined as: ‘Action taken to identify patient at risk of overmedicalization, to protect him from new medical invasion, and to suggest to him interventions, which are ethically acceptable.’ The concept of quaternary prevention was initially proposed by Marc Jamoulle and the targets were mainly patients with illness but without a disease. Objectives: The purpose of this opinion article is to open the debate around a new possible definition and a new conceptual model of quaternary prevention based on the belief that quaternary prevention should be present in physicians’ minds for every intervention they suggest to a patient. Discussion: The debate around quaternary prevention is vital in the context of contemporary medicine and has expanded worldwide. The human being may suffer harm from medical interventions from conception, during their childhood, during their entire healthy lifetime as well as during a self-limited disease, a chronic disease, or a terminal disease. The current definition of quaternary prevention has limitations because it excludes patients and medical interventions where a quaternary prevention perspective would be needed and useful to protect patients from harm. In this context, a new definition and conceptual model of quaternary prevention is proposed. Conclusion: In this new proposal, quaternary prevention is defined as an ‘action taken to protect individuals (persons/patients) from medical interventions that are likely to cause more harm than good.’ PMID:29384397

A library of atomically thin metal chalcogenides.

PubMed

Zhou, Jiadong; Lin, Junhao; Huang, Xiangwei; Zhou, Yao; Chen, Yu; Xia, Juan; Wang, Hong; Xie, Yu; Yu, Huimei; Lei, Jincheng; Wu, Di; Liu, Fucai; Fu, Qundong; Zeng, Qingsheng; Hsu, Chuang-Han; Yang, Changli; Lu, Li; Yu, Ting; Shen, Zexiang; Lin, Hsin; Yakobson, Boris I; Liu, Qian; Suenaga, Kazu; Liu, Guangtong; Liu, Zheng

2018-04-01

Investigations of two-dimensional transition-metal chalcogenides (TMCs) have recently revealed interesting physical phenomena, including the quantum spin Hall effect 1,2 , valley polarization 3,4 and two-dimensional superconductivity 5 , suggesting potential applications for functional devices 6-10 . However, of the numerous compounds available, only a handful, such as Mo- and W-based TMCs, have been synthesized, typically via sulfurization 11-15 , selenization 16,17 and tellurization 18 of metals and metal compounds. Many TMCs are difficult to produce because of the high melting points of their metal and metal oxide precursors. Molten-salt-assisted methods have been used to produce ceramic powders at relatively low temperature 19 and this approach 20 was recently employed to facilitate the growth of monolayer WS 2 and WSe 2 . Here we demonstrate that molten-salt-assisted chemical vapour deposition can be broadly applied for the synthesis of a wide variety of two-dimensional (atomically thin) TMCs. We synthesized 47 compounds, including 32 binary compounds (based on the transition metals Ti, Zr, Hf, V, Nb, Ta, Mo, W, Re, Pt, Pd and Fe), 13 alloys (including 11 ternary, one quaternary and one quinary), and two heterostructured compounds. We elaborate how the salt decreases the melting point of the reactants and facilitates the formation of intermediate products, increasing the overall reaction rate. Most of the synthesized materials in our library are useful, as supported by evidence of superconductivity in our monolayer NbSe 2 and MoTe 2 samples 21,22 and of high mobilities in MoS 2 and ReS 2 . Although the quality of some of the materials still requires development, our work opens up opportunities for studying the properties and potential application of a wide variety of two-dimensional TMCs.

Salt precipitation and dissolution in the late Quaternary Dead Sea: Evidence from chemical and δ37Cl composition of pore fluids and halites

NASA Astrophysics Data System (ADS)

Levy, Elan J.; Yechieli, Yoseph; Gavrieli, Ittai; Lazar, Boaz; Kiro, Yael; Stein, Mordechai; Sivan, Orit

2018-04-01

The chemical composition and δ37Cl of pore fluids from the ICDP core drilled in the deepest floor of the terminal and hypersaline Dead Sea, and halites from the adjacent Mount Sedom salt diapir, are used to establish the dynamics of halite precipitation and dissolution during the last interglacial and glacial periods. Between ∼132 and 116 thousand years ago (ka) halites precipitated in the lake resulting in the expulsion of Na+ and Cl- from the residual solution. Over 50% of the Cl- reservoir was removed, resulting in a decrease in the Na/Cl ratio from 0.57 to 0.19. This process was accompanied by a decrease in δ37Cl values in the precipitating halites and the associated residual Cl- in the lake. The observed decrease fits a Rayleigh distillation curve with a fractionation factor of Δ(NaCl-Dead Sea solution) = +0.32‰ (±0.12) determined in the present study. This behavior implies negligible contribution of external sources of Cl- to the lake during the main peak of the last interglacial, MIS5e. Subsequently, during the last glacial (ca. 117 to 17 ka) dissolution of halite took place, the Na+ and Cl- inventory were replenished, accompanied by an increase in Na/Cl from 0.21 to 0.55 and in the δ37Cl values from -0.46‰ to -0.12‰. While the lake underwent significant dilution during that time, the decrease in salinity was somewhat suppressed by the dissolution of the halite which was mostly derived from Mount Sedom salt diapir.

Virucidal agents in the eve of manorapid synergy®

PubMed Central

Galabov, Angel S.

2007-01-01

Virucidal agents are chemical substances that attack and inactivate viral particles outside the cell (virions). In general this is accomplished by damaging their protein shells (capsid) or the substance penetrates the core itself, where it destroys the genetic material. Damage to the virion structure is also possible. These agents are used not only for traditional surface disinfection or sterilization of blood, blood products, and other medicinal products as well as in antiviral chemotherapy. They have also been used in recent times for inactivation of viruses in foodstuffs, detergents or cosmetics. Below is given an overview of the data currently available on the performance of these substances when used for the latter applications (cleaning and cosmetics). These include: hydrogen peroxide, hypochlorites, cupric and ferric ions, per-acids ethanol, parachlorometaxylenol in a sodium C14-16 olefin sulfonate, glutaraldehyde, quaternary ammonium salts, chlorhexidine and chlorhexidine gluconate, curdline sulphate, glycerol, lipids, azodicarbonamide, cicloxolone sodium, dichlorisocyanuric acid (sodium salt), benzalkonium salts, disulfate benzamides and benzisothiazolones, congo red, ascorbic acid, nonoxynol-9, para-aminobenzoic acid, bis(monosuccinamide) derivative of p,p’-bis(2-aminoethyl) diphenlyi-C60) (fullerene). merocyanine, benzoporphyrin derivative monoacid ring A, rose bengal, hypericin, hypocrellin A, anthraquinones extracted from plants, sulfonated anthraquinones and other anthraquinone derivatives gramicidine, gossypol, garlic (Allium sativum) extract and its components: ajoene, diallyl thiosulfinate (allicin), allyl methyl thioulfinate, methyl allyl thiosulfinate, extracts of ledium, motherworth, celandine, black currant, coaberry and bilberry, extract of Cordia salicifolia, steam distillate from Houttuynia cordata (Saururaceae) and its component, 5,6,7-trimethoxyflavone from Calicarpa japonica, isoscullarein (5,7,8,4’-tetrahydroxyflavone) from Scutellaria baikalensis and isoscutellarein-8-methylether, alkaloids and phytosteryl ester compounds. PMID:20200679

Publications - MP 141 | Alaska Division of Geological & Geophysical Surveys

Science.gov Websites

DGGS MP 141 Publication Details Title: Quaternary faults and folds in Alaska: A digital database Combellick, R.A., 2012, Quaternary faults and folds in Alaska: A digital database, in Koehler, R.D Quaternary faults, scale 1:3,700,000 (63.0 M) Digital Geospatial Data Digital Geospatial Data Quaternary

Advances in the Fabrication of Antimicrobial Hydrogels for Biomedical Applications.

PubMed

González-Henríquez, Carmen M; Sarabia-Vallejos, Mauricio A; Rodriguez-Hernandez, Juan

2017-02-26

This review describes, in an organized manner, the recent developments in the elaboration of hydrogels that possess antimicrobial activity. The fabrication of antibacterial hydrogels for biomedical applications that permits cell adhesion and proliferation still remains as an interesting challenge, in particular for tissue engineering applications. In this context, a large number of studies has been carried out in the design of hydrogels that serve as support for antimicrobial agents (nanoparticles, antibiotics, etc.). Another interesting approach is to use polymers with inherent antimicrobial activity provided by functional groups contained in their structures, such as quaternary ammonium salt or hydrogels fabricated from antimicrobial peptides (AMPs) or natural polymers, such as chitosan. A summary of the different alternatives employed for this purpose is described in this review, considering their advantages and disadvantages. Finally, more recent methodologies that lead to more sophisticated hydrogels that are able to react to external stimuli are equally depicted in this review.

Advances in the Fabrication of Antimicrobial Hydrogels for Biomedical Applications

PubMed Central

González-Henríquez, Carmen M.; Sarabia-Vallejos, Mauricio A.; Rodriguez-Hernandez, Juan

2017-01-01

This review describes, in an organized manner, the recent developments in the elaboration of hydrogels that possess antimicrobial activity. The fabrication of antibacterial hydrogels for biomedical applications that permits cell adhesion and proliferation still remains as an interesting challenge, in particular for tissue engineering applications. In this context, a large number of studies has been carried out in the design of hydrogels that serve as support for antimicrobial agents (nanoparticles, antibiotics, etc.). Another interesting approach is to use polymers with inherent antimicrobial activity provided by functional groups contained in their structures, such as quaternary ammonium salt or hydrogels fabricated from antimicrobial peptides (AMPs) or natural polymers, such as chitosan. A summary of the different alternatives employed for this purpose is described in this review, considering their advantages and disadvantages. Finally, more recent methodologies that lead to more sophisticated hydrogels that are able to react to external stimuli are equally depicted in this review. PMID:28772591

Structure, wettability and thermal degradation of new fluoro-oligomer modified nanoclays.

PubMed

Valsecchi, R; Viganò, M; Levi, M; Turri, S

2008-04-01

Quaternary ammonium salts based on monofunctionalized Perfluoropolyether (PFPE) oligomers were synthesized and used for the cation exchange process of sodium Montmorillonite nanoclays. The new fluoromodified nanoclays were characterized through X-rays diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), termogravimetric analysis (TGA), differential scanning calorimetry (DSC), electronic microscopy (SEM-EDS), and contact angle measurements (CA). In particular XRD showed rather complex patterns (presence of higher order reflections) which allowed the calculation of basal spacings, regularly increasing with the molecular weight of the fluorinated macrocation. Both IR and SEM confirmed the presence of fluorinated segments at clays interface, while TGA showed a limited thermal stability with an onset of degradation temperature which seems not dependent on the molecular weight of the macrocation. CA measurements showed a peculiar behaviour, with evident dynamic hysteresis phenomena and surface tension components quite different from those of commercially available, organomodified clays.

In vitro evaluation of the disinfection efficacy on Eimeria tenella unsporulated oocysts isolated from broilers.

PubMed

Guimarães, José S; Bogado, Alexey L Gomel; da Cunha, Thiago Cezar B; Garcia, João Luis

2007-01-01

The objective of this study was to evaluate in vitro the action of eight chemical principles by disinfection efficacy (DE) of Eimeria tenella oocysts. Disinfection efficacy was evaluated by either destruction or sporulation inhibition of the oocysts. Eight treatments were performed: T1 (Glutaraldehyde 42.5 g + Benzalkonium Chloride 7.5 g); T2 (Benzalkonium chloride + quaternary ammonium salt); T3 (formol 37% + Sodium Dodecylbenzene Sulfonate 12%); T4 (sodium hypochlorite 2%); T5 (Orthodichlorobenzene 60% + Xylene 30%); T6 (Polyoctyl polyamino ethyl glycine + Polyoxyethylene alkylphenol ether + Sodium Chloride); T7 (Chloramine T) and finally T8 (free iodine 2.25% + Phosphoric acid 15 g). The control test was carried out with distilled water (T9). The best DE were observed, respectively, in T3 (79.49%), T5 (75.60%) and T4 (65.56%) treatments.

Mineral resources of the Little Black Peak and Carrizozo Lava Flow wilderness study areas, Lincoln County, New Mexico

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stoeser, D.B.; Senterfit, M.K.; Zelten, J.E.

1989-01-01

This book discusses the Little Black Peak and Carrizozo Lava Flow Wilderness Study Areas in east-central New Mexico (24,249 acres) which are underlain by Quaternary basaltic lava flows and upper Paleozoic to Mesozoic sedimentary rocks. The only identified resource is lava from the basalt flows, which is used for road metal, construction materials, and decorative stone. The basalt is classed as an inferred subeconomic resource. Both areas have low resource potential for sediment-hosted uranium and copper oil, gas, coal, and geothermal energy and moderate potential for gypsum and salt. The Little Black Peak area also has low potential for uraniummore » associated with Tertiary alkaline intrusive rocks. Two aeromagnetic anomalies occur beneath the northern part of the Carrizozo lava flow area and the southern part of the Little Black Peak area; the resource potential for these rocks is unknown.« less

Sol-gel hybrid films based on organosilane and montmorillonite for corrosion inhibition of AA2024.

PubMed

Dalmoro, V; dos Santos, J H Z; Armelin, E; Alemán, C; Azambuja, D S

2014-07-15

The present work reports the production of films on AA2024-T3 composed of vinyltrimethoxysilane (VTMS)/tetraethylorthosilicate (TEOS) with incorporation of montmorillonite (sodium montmorillonite and montmorillonite modified with quaternary ammonium salt, abbreviated Na and 30B, respectively), generated by the sol-gel process. According to FT-IR analyses the incorporation of montmorillonite does not affect silica network. Electrochemical characterization was performed by electrochemical impedance spectroscopy measurement in 0.05 mol L(-1) NaCl solution. Results indicate that montmorillonite incorporation improves the corrosion protection compared to the non-modified system. Scanning electron microscopy micrographs reveal that high concentrations of montmorillonite provide agglomerations on the metallic surface, which is in detriment of the anticorrosive performance. The VTMS/TEOS/30B films with the lowest concentration (22 mg L(-1)) of embedded clay provide the highest corrosion protection. Copyright © 2014 Elsevier Inc. All rights reserved.

Evidence of the Zanclean megaflood in the eastern Mediterranean Basin.

PubMed

Micallef, Aaron; Camerlenghi, Angelo; Garcia-Castellanos, Daniel; Cunarro Otero, Daniel; Gutscher, Marc-André; Barreca, Giovanni; Spatola, Daniele; Facchin, Lorenzo; Geletti, Riccardo; Krastel, Sebastian; Gross, Felix; Urlaub, Morelia

2018-01-18

The Messinian salinity crisis (MSC) - the most abrupt, global-scale environmental change since the end of the Cretaceous - is widely associated with partial desiccation of the Mediterranean Sea. A major open question is the way normal marine conditions were abruptly restored at the end of the MSC. Here we use geological and geophysical data to identify an extensive, buried and chaotic sedimentary body deposited in the western Ionian Basin after the massive Messinian salts and before the Plio-Quaternary open-marine sedimentary sequence. We show that this body is consistent with the passage of a megaflood from the western to the eastern Mediterranean Sea via a south-eastern Sicilian gateway. Our findings provide evidence for a large amplitude drawdown in the Ionian Basin during the MSC, support the scenario of a Mediterranean-wide catastrophic flood at the end of the MSC, and suggest that the identified sedimentary body is the largest known megaflood deposit on Earth.

Catalytic enantioselective synthesis of indanes by a cation-directed 5-endo-trig cyclization.

PubMed

Johnston, Craig P; Kothari, Abhishek; Sergeieva, Tetiana; Okovytyy, Sergiy I; Jackson, Kelvin E; Paton, Robert S; Smith, Martin D

2014-02-01

5-Endo-trig cyclizations are generally considered to be kinetically unfavourable, as described by Baldwin's rules. Consequently, observation of this mode of reaction under kinetic control is rare. This is usually ascribed to challenges in achieving appropriate approach trajectories for orbital overlap in the transition state. Here, we describe a highly enantio- and diastereoselective route to complex indanes bearing all-carbon quaternary stereogenic centres via a 5-endo-trig cyclization catalysed by a chiral ammonium salt. Through computation, the preference for the formally disfavoured 5-endo-trig Michael reaction over the formally favoured 5-exo-trig Dieckmann reaction is shown to result from thermodynamic contributions to the innate selectivity of the nucleophilic group, which outweigh the importance of the approach trajectory as embodied by Baldwin's rules. Our experimental and theoretical findings demonstrate that geometric and stereoelectronic constraints may not be decisive in the observed outcome of irreversible ring-closing reactions.

Integrated process for the removal of emulsified oils from effluents in the steel industry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Benito, J.M.; Rios, G.; Gutierrez, B.

1999-11-01

Emulsified oils contained in aqueous effluents from cold-rolling mills of the steel industry can be effectively removed via an integrated process consisting of a coagulation/flocculation stage followed by ultrafiltration of the resulting aqueous phase. The effects of CaCl{sub 2}, NaOH, and lime on the stability of different industrial effluents were studied in the coagulation experiments. The flocculants tested were inorganic prehydrolyzed aluminum salts and quaternary polyamines. Ultrafiltration of the aqueous phase from the coagulation/flocculation stage was carried out in a stirred cell using Amicon PM30 and XM300 organic membranes. Permeate fluxes were measured for industrial effluents to which the indicatedmore » coagulants and flocculants had been added. Oil concentrations in the permeate were 75% lower than the limits established by all European Union countries. Complete regeneration of the membrane was accomplished with an aqueous solution of a commercial detergent.« less

13C NMR and XPS characterization of anion adsorbent with quaternary ammonium groups prepared from rice straw, corn stalk and sugarcane bagasse

NASA Astrophysics Data System (ADS)

Cao, Wei; Wang, Zhenqian; Zeng, Qingling; Shen, Chunhua

2016-12-01

Despite amino groups modified crop straw has been intensively studied as new and low-cost adsorbent for removal of anionic species from water, there is still a lack of clear characterization for amino groups, especially quaternary ammonium groups in the surface of crop straw. In this study, we used 13C NMR and XPS technologies to characterize adsorbents with quaternary ammonium groups prepared from rice straw, corn stalk and sugarcane bagasse. 13C NMR spectra clearly showed the presence of quaternary ammonium groups in lignocelluloses structure of modified crop straw. The increase of nitrogen observed in XPS survey spectra also indicated the existence of quaternary ammonium group in the surface of the adsorbents. The curve fitting of high-resolution XPS N1s and C1s spectra were conducted to probe the composition of nitrogen and carbon contained groups, respectively. The results showed the proportion of quaternary ammonium group significantly increased in the prepared adsorbent's surface that was dominated by methyl/methylene, hydroxyl, quaternary ammonium, ether and carbonyl groups. This study proved that 13C NMR and XPS could be successfully utilized for characterization of quaternary ammonium modified crop straw adsorbents.

Comparison of GPS and Quaternary slip rates: Insights from a new Quaternary fault database for Central Asia

NASA Astrophysics Data System (ADS)

Mohadjer, Solmaz; Ehlers, Todd; Bendick, Rebecca; Mutz, Sebastian

2016-04-01

Previous studies related to the kinematics of deformation within the India-Asia collision zone have relied on slip rate data for major active faults to test kinematic models that explain the deformation of the region. The slip rate data, however, are generally disputed for many of the first-order faults in the region (e.g., Altyn Tagh and Karakorum faults). Several studies have also challenged the common assumption that geodetic slip rates are representative of Quaternary slip rates. What has received little attention is the degree to which geodetic slip rates relate to Quaternary slip rates for active faults in the India-Asia collision zone. In this study, we utilize slip rate data from a new Quaternary fault database for Central Asia to determine the overall relationship between Quaternary and GPS-derived slip rates for 18 faults. The preliminary analysis investigating this relationship uses weighted least squares and a re-sampling analysis to test the sensitivity of this relationship to different data point attributes (e.g., faults associated with data points and dating methods used for estimating Quaternary slip rates). The resulting sample subsets of data points yield a maximum possible Pearson correlation coefficient of ~0.6, suggesting moderate correlation between Quaternary and GPS-derived slip rates for some faults (e.g., Kunlun and Longmen Shan faults). Faults with poorly correlated Quaternary and GPS-derived slip rates were identified and dating methods used for the Quaternary slip rates were examined. Results indicate that a poor correlation between Quaternary and GPS-derived slip rates exist for the Karakorum and Chaman faults. Large differences between Quaternary and GPS slip rates for these faults appear to be connected to qualitative dating of landforms used in the estimation of the Quaternary slip rates and errors in the geomorphic and structural reconstruction of offset landforms (e.g., offset terrace riser reconstructions for Altyn Tagh fault). Other factors such as a low density in the GPS network (e.g., GPS rate based on data from a single station for the Karakorum fault) appear to also contribute to the mismatch observed between the slip rates. Taken together, these results suggest that GPS-derived slip rates are often (but not always) representative of Quaternary slip rates and that the dating methods and sampling approaches used to identify transients in a fault slip rate history should be heavily scrutinized before interpreting the seismic hazards for a region.

Exceptionally Strong Electron-Donating Ability of Bora-Ylide Substituent vis-à-vis Silylene and Silylium Ion.

PubMed

Rosas-Sánchez, Alfredo; Alvarado-Beltran, Isabel; Baceiredo, Antoine; Saffon-Merceron, Nathalie; Massou, Stéphane; Branchadell, Vicenç; Kato, Tsuyoshi

2017-08-21

Electropositive boron-based substituent (phosphonium bora-ylide) with an exceptionally strong π- and σ-electron donating character dramatically increases the stability of a new type of N-heterocyclic silylene 2 featuring amino- and bora-ylide-substituents. Moreover, the related silylium ion 4 and transition-metal-silylene complexes, with trigonal-planar geometries around the silicon center, are also well stabilized. Therefore, the N,B-heterocyclic silylene 2 can be used as a strongly electron-donating innocent ligand in coordination chemistry similarly to N-heterocyclic carbenes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Induction of Intracellular Reductive Stress with a Photoactivatable Phosphine Probe.

PubMed

Tirla, Alina; Rivera-Fuentes, Pablo

2018-04-25

Reductive stress is a condition present in cells that have an increased concentration of reducing species, and it has been associated with a number of pathologies, such as neurodegenerative diseases and cancer. The tools available to study reductive stress lack both in selectivity and specific targeting and some of these shortcomings can be addressed by using photoactivatable compounds. We developed a photoactivatable phosphonium probe, which upon irradiation releases a fluorescent molecule and a trialkyphosphine. The probes can permeate through the plasma membrane and the photoreleased phosphine can induce intracellular reductive stress as proven by the detection of protein aggregates.

Thermochemical tests on resins: Char resistance of selected phenolic cured epoxides

NASA Technical Reports Server (NTRS)

Keck, F. L.

1982-01-01

Curing epoxy resins with novalac phenolic resins is a feasible approach for increasing intact char of the resin system. Char yields above 40% at 700 C were achieved with epoxy novalac (DEN 438)/novalac phenolic (BRWE 5833) resin systems with or without catalyst such as ethyl tri-phenyl phosphonium iodide. These char yields are comparable to commercially used epoxy resin systems like MY-720/DDS/BF3. Stable prepregs are easily made from a solvent solution of the epoxy/phenolic system and this provides a feasible process for fabrication of same into commercial laminates.

A tsunami deposit from Vancouver Island, Canada ― Geological evidence for the penultimate great Cascadia earthquake?

NASA Astrophysics Data System (ADS)

Tanigawa, K.; Sawai, Y.; Bobrowsky, P. T.; Huntley, D.; Goff, J. R.; Shinozaki, T.

2017-12-01

We examined tsunami deposits within salt marshes at Tofino, Ucluelet and Port Alberni along the west coast of Vancouver Island aligned with the Cascadia Subduction Zone. Previous studies in 1990s reported tsunami deposits associated with the 1964 Alaska, the 1700 Cascadia and older earthquakes from these sites (Clague and Bobrowsky, 1994a; b). However, the ages of older tsunami deposits were not well constrained. We excavated pits and collected salt marsh sediments in 2015 and 2016. Sand layers interbedded within peat and mud deposits occur at widely separated sites on Vancouver Island. Two visible sand layers were observed in Tofino, four in Ucluelet and three in Port Alberni; which is consistent with previous studies. We used a combination of 210Pb, 137Cs and 14C dating to constrain the depositional ages of sand layers. Plant microfossils and insects obtained directly above and below each sand layer were used for radiocarbon dating. Radiocarbon ages indicate that the sand layer prior to the 1700 tsunami sediments was deposited between 550-300 calendar years before present. This depositional age is correlative to the T2 event of the Cascadia Subduction Zone turbidite history (Goldfinger et al., 2012). References: Clague and Bobrowsky (1994a) Quaternary Research, 41, 176-184. Clague and Bobrowsky (1994b) GSA Bulletin 106, 1293-1303. Goldfinger et al. (2012) USGS Professional Paper 1661-F, 170 p.

A kryptoracemic salt: 2-{[2,8-bis-(tri-fluoro-meth-yl)quinolin-4-yl](hy-droxy)meth-yl}piperidin-1-ium (+)-3,3,3-tri-fluoro-2-meth-oxy-2-phenyl-propanoate.

PubMed

Wardell, James L; Wardell, Solange M S V; Tiekink, Edward R T

2016-06-01

The asymmetric unit of the title salt, C17H17F6N2O(+)·C10H8F3O3 (-), comprises two piperidin-1-ium cations and two carboxyl-ate anions. The cations, each having an l-shaped conformation owing to the near orthogonal relationship between the quinolinyl and piperidin-1-ium residues, are pseudo-enanti-omeric. The anions have the same absolute configuration but differ in the relative orientations of the carboxyl-ate, meth-oxy and benzene groups. Arguably, the most prominent difference between the anions occurs about the Cq-Om bond as seen in the Cc-Cq-Om-Cm torsion angles of -176.1 (3) and -67.1 (4)°, respectively (q = quaternary, m = meth-oxy and c = carboxyl-ate). The presence of Oh-H⋯Oc and Np-H⋯Oc hydrogen bonds leads to the formation of a supra-molecular chain along the a axis (h = hy-droxy and p = piperidin-1-ium); weak intra-molecular Np-H⋯Oh hydrogen bonds are also noted. Chains are connected into a three-dimensional architecture by C-H⋯F inter-actions. Based on a literature survey, related mol-ecules/cations adopt a uniform conformation in the solid state based on the letter L.

Salts employed in hydrophobic interaction chromatography can change protein structure - insights from protein-ligand interaction thermodynamics, circular dichroism spectroscopy and small angle X-ray scattering.

PubMed

Komaromy, Andras Z; Kulsing, Chadin; Boysen, Reinhard I; Hearn, Milton T W

2015-03-01

Key requirements of protein purification by hydrophobic interaction chromatography (HIC) are preservation of the tertiary/quaternary structure, maintenance of biological function, and separation of the correctly folded protein from its unfolded forms or aggregates. This study examines the relationship between the HIC retention behavior of hen egg white lysozyme (HEWL) in high concentrations of several kosmotropic salts and its conformation, assessed by circular dichroism (CD) spectroscopy. Further, the physicochemical properties of HEWL in the presence of high concentrations of ammonium sulfate, sodium chloride and magnesium chloride were investigated by small angle X-ray scattering (SAXS) at different temperatures. Radii of gyration were extrapolated from Guinier approximations and the indirect transform program GNOM with protein-protein interaction and contrast variation taken into account. A bead model simulation provided information on protein structural changes using ab initio reconstruction with GASBOR. These results correlated to the secondary structure content obtained from CD spectroscopy of HEWL. These changes in SAXS and CD data were consistent with heat capacity ΔCp -values obtained from van't Hoff plot analyses of the retention data. Collectively, these insights enable informed decisions to be made on the choice of chromatographic conditions, leading to improved separation selectivity and opportunities for innovative column-assisted protein refolding methods. Copyright © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ground water in Tooele Valley, Tooele County, Utah

USGS Publications Warehouse

Thomas, H.E.

1946-01-01

Tooele Valley is a typical basin of the Basin and Range Province located about 30 miles southwest of Salt Lake City. It is roughly 15 miles long and 10 miles wide and has a population of about 7,000. Bordered on the west by the Stansbury Range, on the east by the Oquirrh Range, and on the south by South Mountain, it opens northward to Great Salt Lake. The bordering mountain ranges are formed by Paleozoic rocks ranging in age from Lower Cambrian to Pennsylvanian but with the Ordovician and Silurian periods unrepresented. There is no sedimentary record of the interval between Pennsylvanian and Tertiary times, and the Tertiary, Quaternary, and Recent sediments are of continental origin. These continental deposits play the dominant role in the ground-water hydrology of the basin, and were mapped and studied in detail. Pleistocene sediments are of major importance because they form the surface rock over most of the area, and give rise to conditions which yield water by artesian flow in the lower part of the valley.The development of the present land forms in this area began with the folding of Paleozoic and probably Mesozoic sediments during the Laramide revolution. The cycle of highland erosion and lowland deposition thus initiated has continued through recurrent uplift along Basin-Range faults to the present day. The principal physiographic subdivisions of the valley were developed as a result of the Basin-Range faulting, which began early in the Tertiary and has continued to Recent times.There are about 1,100 wells in Tooele Valley, about 90 per cent of which yield or have yielded water by artesian flow. Most of them are located in the lower part of the valley below an altitude of 4,400 feet. These wells and many of the springs derive their water from the unconsolidated Quaternary sediments, which include discontinuous, lenticular and commonly elongated bodies of sand, clay, gravel, and boulders of alluvial origin alternating and inter-fingered with lacustrine beds of the same materials which are more regularly stratified and better assorted. The larger springs are intimately related to the bedding planes and faults in the bedrock and alluvial formations. The well assorted sands and gravels deposited along the shore lines of Lake Bonneville are important as recharge areas for the artesian reservoir.

A review on the synthesis, crystal growth, structure and physical properties of rare earth based quaternary intermetallic compounds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mumbaraddi, Dundappa; Sarkar, Sumanta; Peter, Sebastian C., E-mail: sebastiancp@jncasr.ac.in

2016-04-15

This review highlights the synthesis and crystal growth of quaternary intermetallic compounds based on rare earth metals. In the first part of this review, we highlight briefly about intermetallics and their versatile properties in comparison to the constituent elements. In the next part, we have discussed about various synthesis techniques with more focus on the metal flux technique towards the well shaped crystal growth of novel compounds. In the subsequent parts, several disordered quaternary compounds have been reviewed and then outlined most known ordered quaternary compounds with their complex structure. A special attention has been given to the ordered compoundsmore » with structural description and relation to the parent binary and ternary compounds. The importance of electronic and structural feature is highlighted as the key roles in designing these materials for emerging applications. - Graphical abstract: Rare earth based quaternary intermetallic compounds crystallize in complex novel crystal structures. The diversity in the crystal structure may induce unique properties and can be considered them as future materials. - Highlights: • Crystal growth and crystal structure of quaternary rare earth based intermetallics. • Structural complexity of quaternary compounds in comparison to the parent compounds. • Novel quaternary compounds display unique crystal structure.« less

PRN 88-2: Clustering of Quaternary Ammonium Compounds

EPA Pesticide Factsheets

This Notice announces that EPA has clustered the Quaternary Ammonium Compounds into four groups for the purpose of testing chemicals to build a database that will support continued registration of the entire family of quaternary ammonium compounds

Branched-chain dicationic ionic liquids for fatty acid methyl ester assessment by gas chromatography.

PubMed

Talebi, Mohsen; Patil, Rahul A; Sidisky, Leonard M; Berthod, Alain; Armstrong, Daniel W

2017-12-06

Twelve bis- or dicationic ionic liquids (ILs) including eight based on imidazolium, a single one based on phosphonium, and three based on pyrrolidinium cationic units were prepared with the bis(trifluoromethyl sulfonyl) imide anion. The two identical cationic moieties were attached by different alkyl spacers having three or five carbons and differing alkyl substituents attached to the spacer. The SLB-IL111 column, as the most polar commercial stationary phase known, was included in the study for comparison. Isothermal separations of a rapeseed oil fatty acid methyl ester (FAME) sample were used to study and compare the 12 IL-based column performances and selectivities. The retention times of the most retained methyl esters of lignoceric (C24:0) and erucic (C22:1) acids were used to estimate the IL polarity. The phosphonium dicationic IL column was, by far, the least polar. Imidazolium-based dicationic IL columns were the most polar. Polarity and selectivity for the FAME separation were somewhat related. The separation of a 37-FAME standard mixture allowed the investigation of selectivity variations observed on the 12 IL-based columns under temperature gradients up to 230 °C. The remarkable selectivity of the IL-based columns is demonstrated by the detailed analysis of the cis/trans C18:1 isomers of a partially hydrogenated vegetable oil sample on 30-m columns, separations competing with that done following an "official method" performed on a 100-m column. Graphical abstract Separation of fatty acid methyl esters on a 30-m 3m 2 C 5 (mpy) 2 . 2NTf 2 branched-chain dicationic IL-based column. Branched chain dicationic ILs show great selectivity for separation of cis/trans, ω-3/ω-6, and detailed analysis of cis/trans fats.

New insights into the thermal behaviour of organic ionic plastic crystals: magnetic resonance imaging of polycrystalline morphology alterations induced by solid-solid phase transitions.

PubMed

Romanenko, Konstantin; Pringle, Jennifer M; O'Dell, Luke A; Forsyth, Maria

2015-07-15

Organic ionic plastic crystals (OIPCs) show strong potential as solid-state electrolytes for lithium battery applications, demonstrating promising electrochemical performance and eliminating the need for a volatile and flammable liquid electrolyte. The ionic conductivity (σ) in these systems has recently been shown to depend strongly on polycrystalline morphology, which is largely determined by the sample's thermal history. [K. Romanenko et al., J. Am. Chem. Soc., 2014, 136, 15638]. Tailoring this morphology could lead to conductivities sufficiently high for battery applications, so a more complete understanding of how phenomena such as solid-solid phase transitions can affect the sample morphology is of significant interest. Anisotropic relaxation of nuclear spin magnetisation provides a new MRI based approach for studies of polycrystalline materials at both a macroscopic and molecular level. In this contribution, morphology alterations induced by solid-solid phase transitions in triisobutyl(methyl)phosphonium bis(fluorosulfonyl)imide (P1444FSI) and diethyl(methyl)(isobutyl)phosphonium hexafluorophosphate (P1224PF6) are examined using magnetic resonance imaging (MRI), alongside nuclear magnetic resonance (NMR) spectroscopy, diffusion measurements and conductivity data. These observations are linked to molecular dynamics and structural behaviour crucial for the conductive properties of OIPCs. A distinct correlation is established between the conductivity at a given temperature, σ(T), and the intensity of the narrow NMR signal that is attributed to a mobile fraction, fm(T), of ions in the OIPC. To explain these findings we propose an analogy with the well-studied relationship between permeability (k) and void fraction (θ) in porous media, with k(θ) commonly quantified by a power-law dependence that can also be employed to describe σ(fm).

Simultaneously Tailoring Surface Energies and Thermal Stabilities of Cellulose Nanocrystals Using Ion Exchange: Effects on Polymer Composite Properties for Transportation, Infrastructure, and Renewable Energy Applications.

PubMed

Fox, Douglas M; Rodriguez, Rebeca S; Devilbiss, Mackenzie N; Woodcock, Jeremiah; Davis, Chelsea S; Sinko, Robert; Keten, Sinan; Gilman, Jeffrey W

2016-10-12

Cellulose nanocrystals (CNCs) have great potential as sustainable reinforcing materials for polymers, but there are a number of obstacles to commercialization that must first be overcome. High levels of water absorption, low thermal stabilities, poor miscibility with nonpolar polymers, and irreversible aggregation of the dried CNCs are among the greatest challenges to producing cellulose nanocrystal-polymer nanocomposites. A simple, scalable technique to modify sulfated cellulose nanocrystals (Na-CNCs) has been developed to address all of these issues. By using an ion exchange process to replace Na + with imidazolium or phosphonium cations, the surface energy is altered, the thermal stability is increased, and the miscibility of dried CNCs with a nonpolar polymer (epoxy and polystyrene) is enhanced. Characterization of the resulting ion exchanged CNCs (IE-CNCs) using potentiometry, inverse gas chromatography, dynamic vapor sorption, and laser scanning confocal microscopy reveals that the IE-CNCs have lower surface energies, adsorb less water, and have thermal stabilities of up to 100 °C higher than those of prepared protonated cellulose nanocrystals (H-CNCs) and 40 °C higher than that of neutralized Na-CNC. Methyl(triphenyl)phosphonium exchanged cellulose nanocrystals (MePh 3 P-CNC) adsorbed 30% less water than Na-CNC, retained less water during desorption, and were used to prepare well-dispersed epoxy composites without the aid of a solvent and well-dispersed polystyrene nanocomposites using a melt blending technique at 195 °C. Predictions of dispersion quality and glass transition temperatures from molecular modeling experiments match experimental observations. These fiber-reinforced polymers can be used as lightweight composites in transportation, infrastructure, and renewable energy applications.

OMVPE Growth of Quaternary (Al,Ga,In)N for UV Optoelectronics (title change from A)

DOE Office of Scientific and Technical Information (OSTI.GOV)

HAN,JUNG; FIGIEL,JEFFREY J.; PETERSEN,GARY A.

We report the growth and characterization of quaternary AlGaInN. A combination of photoluminescence (PL), high-resolution x-ray diffraction (XRD), and Rutherford backscattering spectrometry (RBS) characterizations enables us to explore the contours of constant PL peak energy and lattice parameter as functions of the quaternary compositions. The observation of room temperature PL emission at 351nm (with 20% Al and 5% In) renders initial evidence that the quaternary could be used to provide confinement for GaInN (and possibly GaN). AlGaInN/GrdnN MQW heterostructures have been grown; both XRD and PL measurements suggest the possibility of incorporating this quaternary into optoelectronic devices.

Database and Map of Quaternary Faults and Folds in Peru and its Offshore Region

USGS Publications Warehouse

Machare, Jose; Fenton, Clark H.; Machette, Michael N.; Lavenu, Alain; Costa, Carlos; Dart, Richard L.

2003-01-01

This publication consists of a main map of Quaternary faults and fiolds of Peru, a table of Quaternary fault data, a region inset map showing relative plate motion, and a second inset map of an enlarged area of interest in southern Peru. These maps and data compilation show evidence for activity of Quaternary faults and folds in Peru and its offshore regions of the Pacific Ocean. The maps show the locations, ages, and activity rates of major earthquake-related features such as faults and fault-related folds. These data are accompanied by text databases that describe these features and document current information on their activity in the Quaternary.

Quaternary Geologic Map of Connecticut and Long Island Sound Basin

USGS Publications Warehouse

Stone, Janet Radway; Schafer, John P.; London, Elizabeth Haley; DiGiacomo-Cohen, Mary L.; Lewis, Ralph S.; Thompson, Woodrow B.

2005-01-01

The Quaternary geologic map (sheet 1) and explanatory figures and cross sections (sheet 2) portray the geologic features formed in Connecticut during the Quaternary Period, which includes the Pleistocene (glacial) and Holocene (postglacial) Epochs. The Quaternary Period has been a time of development of many details of the landscape and of all the surficial deposits. At least twice in the late Pleistocene, continental ice sheets swept across Connecticut. Their effects are of pervasive importance to the present occupants of the land. The Quaternary geologic map illustrates the geologic history and the distribution of depositional environments during the emplacement of glacial and postglacial surficial deposits and the landforms resulting from those events.

3D structure of a complex of transform basins from gravity data, a case study from the central Dead Sea fault

NASA Astrophysics Data System (ADS)

Rosenthal, Michal; Schattner, Uri; Ben-Avraham, Zvi

2017-04-01

The Kinneret-Bet She'an (KBS) basin complex comprises the Sea of Galilee, Kinarot, and Bet She'an sub-basins. The complex developed at the intersection between two major tectonic boundaries: the Oligo-Miocene Azraq-Sirhan failed rift, that later developed into the southern Galilee basins and Carmel-Gilboa fault system; and the Dead Sea fault (DSF) plate boundary that developed since the Miocene. Despite numerous studies, KBS still remains one of the enigmatic basin complexes. Its structure, stratigraphy and development are vaguely understood - both inside the basin and in correlation with its surroundings. Our study presents a new and comprehensive 3D model for the structure of KBS complex. It is based on all available gravity measurements, adopted from the national gravity database, and new gravity measurements, collected in cooperation with the Geological Survey of Israel and funded by the Ministry of National Infrastructure, Energy and Water Resources. The gravity data were integrated with constraints from boreholes, surface geology, seismic surveys, potential field studies and teleseismic tomography. The dense distribution of gravity data [1] provides suitable coverage for modeling the deep structure in three dimensions. The model details the spatial distribution, depth, thickness and density of the following regional units within the KBS complex and across its surroundings: upper crust, pre-Senonian sediments, Senonian and Cenozoic sediments, Miocene volcanics, Pliocene and Quaternary volcanics. Additional local units include salt, gabbro and pyroclasts. Results indicate that the KBS complex comprises two sub-basins separated by a structural saddle: Kinneret-Kinarot ( 6-7 km deep, 45 km long) and Bet She'an ( 4 km deep, 10 km long) sub-basin. A 500 m thick layer of Miocene volcanics appears across the Bet She'an sub-basin, yet missing from the Kinneret-Kinarot sub-basin. Between the basins Zemah-1 borehole penetrated a salt unit. The model indicates that this unit is a part of a thick (1250 m) dome-shaped, perhaps diapiric, structure. A relatively thin (350 m) salt unit fills the Kinneret-Kinarot sub-basin. Above, a 700 m thick layer of Pliocene volcanics fills the entire KBS complex. These volcanics are uplifted in the Zemah area by 200 m. The Pliocene volcanics dip northward from Zemah towards the center of the Sea of Galilee, and further north the Pliocene volcanics dip southward from Korazim towards the center of the Sea of Galilee. The depth differences exceed 3 km across a distance of 15 km, forming a 11° slope below the younger Quaternary fill of the basin. A low-density, probably pyroclastic, lens is calculated within the uppermost 2 km of the Sea of Galilee fill. Scenarios for the development of the basin are discussed. [1] Rosenthal, M., Segev, A., Rybakov, M., Lyakhovsky, V. and Ben-Avraham, Z. (2015) The deep structure and density distribution of northern Israel and its surroundings. GSI Report No. GSI/12/2015, 33 pages, Jerusalem.

Synthesis and anticoagulant activity of the quaternary ammonium chitosan sulfates.

PubMed

Fan, Lihong; Wu, Penghui; Zhang, Jinrong; Gao, Song; Wang, Libo; Li, Mingjia; Sha, Mingming; Xie, Weiguo; Nie, Min

2012-01-01

Quaternary ammonium chitosan sulfates with diverse degrees of substitution (DS) ascribed to sulfate groups between 0.52 and 1.55 were synthesized by reacting quaternary ammonium chitosan with an uncommon sulfating agent (N(SO(3)Na)(3)) that was prepared from sodium bisulfite (NaHSO(3)) through reaction with sodium nitrite (NaNO(2)) in the aqueous system homogeneous. The structures of the derivatives were characterized by FTIR, (1)H NMR and (13)C NMR. The factors affecting DS of quaternary ammonium chitosan sulfates which included the molar ratio of NaNO(2) to quaternary ammonium chitosan, sulfated temperature, sulfated time and pH of sulfated reaction solution were investigated in detail. Its anticoagulation activity in vitro was determined by an activated partial thromboplastin time (APTT) assay, a thrombin time (TT) assay and a prothrombin time (PT) assay. Results of anticoagulation assays showed quaternary ammonium chitosan sulfates significantly prolonged APTT and TT, but not PT, and demonstrated that the introduction of sulfate groups into the quaternary ammonium chitosan structure improved its anticoagulant activity obviously. The study showed its anticoagulant properties strongly depended on its DS, concentration and molecular weight. Crown Copyright © 2011. Published by Elsevier B.V. All rights reserved.

Ionic Liquids as Surfactants for Layered Double Hydroxide Fillers: Effect on the Final Properties of Poly(Butylene Adipate-Co-Terephthalate)

PubMed Central

Livi, Sébastien; Lins, Luanda Chaves; Peter, Jakub; Kredatusova, Jana; Pruvost, Sébastien

2017-01-01

In this work, phosphonium ionic liquids (ILs) based on tetra-alkylphosphonium cations combined with carboxylate, phosphate and phosphinate anions, were used for organic modification of layered double hydroxide (LDH). Two different amounts (2 and 5 wt %) of the organically modified LDHs were mixed with poly(butylene adipate-co-terephthalate) (PBAT) matrix by melt extrusion. All prepared PBAT/IL-modified-LDH composites exhibited increased mechanical properties (20–50% Young’s modulus increase), decreased water vapor permeability (30–50% permeability coefficient reduction), and slight decreased crystallinity (10–30%) compared to the neat PBAT. PMID:28956811

Alkyltributylphosphonium chloride ionic liquids: synthesis, physicochemical properties and crystal structure.

PubMed

Adamová, Gabriela; Gardas, Ramesh L; Nieuwenhuyzen, Mark; Puga, Alberto V; Rebelo, Luís Paulo N; Robertson, Allan J; Seddon, Kenneth R

2012-07-21

A series of alkyltributylphosphonium chloride ionic liquids, prepared from tributylphosphine and the respective 1-chloroalkane, C(n)H(2n+1)Cl (where n = 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12 or 14), is reported. This work is a continuation of an extended series of tetraalkylphosphonium ionic liquids, where the focus is on the variability of n and its impact on the physical properties, such as melting points/glass transitions, thermal stability, density and viscosity. Experimental density and viscosity data were interpreted using QPSR and group contribution methods and the crystal structure of propyl(tributyl)phosphonium chloride is detailed.

Phosphonium-based ionic liquids and their use in the capture of polluting gases

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dai, Sheng; Wang, Congmin; Luo, Huimin

2017-06-06

An ionic liquid composition having the following chemical structural formula: ##STR00001## wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are independently selected from hydrocarbon groups containing at least 1 and up to 20 carbon atoms, and X.sup.- is a cyclic anion that possesses a negatively-charged group reactive with a gaseous electrophilic species, particularly carbon dioxide or sulfur dioxide. Methods for capturing a gaseous electrophilic species, such as CO.sub.2 or SO.sub.2, by contacting the gaseous electrophilic species with an ionic liquid according to Formula (1) are also described.

The role of Quaternary environmental change in plant macroevolution: the exception or the rule?

PubMed Central

Willis, Katherine J; Niklas, Karl J

2004-01-01

The Quaternary has been described as an important time for genetic diversification and speciation. This is based on the premise that Quaternary climatic conditions fostered the isolation of populations and, in some instances, allopatric speciation. However, the 'Quaternary Ice-Age speciation model' rests on two key assumptions: (i) that biotic responses to climate change during the Quaternary were significantly different from those of other periods in Earth's history; and (ii) that the mechanisms of isolation during the Quaternary were sufficient in time and space for genetic diversification to foster speciation. These assumptions are addressed by examining the plant fossil record for the Quaternary (in detail) and for the past 410 Myr, which encompasses previous intervals of icehouse Earth. Our examination of the Quaternary record indicates that floristic responses to climate changes during the past 1.8 Myr were complex and that a distinction has to be made between those plants that were able to withstand the extremes of glacial conditions and those that could not. Generation times are also important as are different growth forms (e.g. herbaceous annuals and arborescent perennials), resulting in different responses in terms of genetic divergence rates during isolation. Because of these variations in the duration of isolation of populations and genomic diversification rates, no canonical statement about the predominant floristic response to climatic changes during the Quaternary (i.e. elevated rates of speciation or extinction, or stasis) is currently possible. This is especially true because of a sampling bias in terms of the fossil record of tree species over that of species with non-arborescent growth forms. Nevertheless, based on the available information, it appears that the dominant response of arborescent species during the Quaternary was extinction rather than speciation or stasis. By contrast, our examination of the fossil record of vascular plants for the past 410 Myr indicates that speciation rates often increased during long intervals of icehouse Earth (spanning up to 50 Myr). Therefore, longer periods of icehouse Earth than those occurring during the Quaternary may have isolated plant populations for sufficiently long periods of time to foster genomic diversification and allopatric speciation. Our results highlight the need for more detailed study of the fossil record in terms of finer temporal and spatial resolution than is currently available to examine the significance of intervals of icehouse Earth. It is equally clear that additional and detailed molecular studies of extant populations of Quaternary species are required in order to determine the extent to which these 'relic' species have genomically diversified across their current populations. PMID:15101573

SE Great Basin Play Fairway Analysis

DOE Data Explorer

Adam Brandt

2015-11-15

Within this submission are multiple .tif images with accompanying metadata of magnetotelluric conductor occurrence, fault critical stress composite risk segment (CRS), permeability CRS, Quaternary mafic extrusions, Quaternary fault density, and Quaternary rhyolite maps. Each of these contributed to a final play fairway analysis (PFA) for the SE Great Basin study area.

Attitudes, perceptions and awareness concerning quaternary prevention among family doctors working in the Social Security System, Peru: a cross-sectional descriptive study.

PubMed

Cuba Fuentes, María Sofía; Zegarra Zamalloa, Carlos Orlando; Reichert, Sonja; Gill, Dawn

2016-04-27

Quaternary Prevention is defined as the action taken to identify patients at risk of overtreatment, to protect them from additional medical treatments, and to suggest interventions that are ethically acceptable. Many countries and organizations have joined in the efforts to practice quaternary prevention. These countries started a campaign called Choosing Wisely that implements recommendations in order to avoid harming patients. To determine the attitudes, perceptions and awareness towards Quaternary Prevention and the practice of “Choosing Wisely Canada Recommendations” among family doctors working in the Social Security System in Peru. A questionnaire was developed after reviewing the literature and contacting experts in the field and was sent by email to all 64 family physicians in the Social Security System (Essalud) in Lima Peru. Responses were received from 40 participants. The response rate was 64%. Approximately 95% reported that they understand the concept of quaternary prevention. Agreement with all the recommendations was 90% or higher. In most of the recommendations the applicability was more than 80%. The most important barriers perceived for the practice of Quaternary Prevention were patients’ expectations (33%). There are positive perceptions towards Quaternary Preventions and Choosing Wisely recommendations in the family doctors of social security in Lima Peru.

High-Throughput Chemical Screening Identifies Compounds that Inhibit Different Stages of the Phytophthora agathidicida and Phytophthora cinnamomi Life Cycles.

PubMed

Lawrence, Scott A; Armstrong, Charlotte B; Patrick, Wayne M; Gerth, Monica L

2017-01-01

Oomycetes in the genus Phytophthora are among the most damaging plant pathogens worldwide. Two important species are Phytophthora cinnamomi , which causes root rot in thousands of native and agricultural plants, and Phytophthora agathidicida , which causes kauri dieback disease in New Zealand. As is the case for other Phytophthora species, management options for these two pathogens are limited. Here, we have screened over 100 compounds for their anti-oomycete activity, as a potential first step toward identifying new control strategies. Our screening identified eight compounds that showed activity against both Phytophthora species. These included five antibiotics, two copper compounds and a quaternary ammonium cation. These compounds were tested for their inhibitory action against three stages of the Phytophthora life cycle: mycelial growth, zoospore germination, and zoospore motility. The inhibitory effects of the compounds were broadly similar between the two Phytophthora species, but their effectiveness varied widely among life cycle stages. Mycelial growth was most successfully inhibited by the antibiotics chlortetracycline and paromomycin, and the quaternary ammonium salt benzethonium chloride. Copper chloride and copper sulfate were most effective at inhibiting zoospore germination and motility, whereas the five antibiotics showed relatively poor zoospore inhibition. Benzethonium chloride was identified as a promising antimicrobial, as it is effective across all three life cycle stages. While further testing is required to determine their efficacy and potential phytotoxicity in planta , we have provided new data on those agents that are, and those that are not, effective against P. agathidicida and P. cinnamomi . Additionally, we present here the first published protocol for producing zoospores from P. agathidicida , which will aid in the further study of this emerging pathogen.

Caves, Carbonates and Climate: Karst Landscape Development through Environmental Forcing, Little Cayman Island

NASA Astrophysics Data System (ADS)

Hsia, S.; Ouellette, G., Jr.; Manfrino, C.

2016-12-01

The Cayman Islands are situated in the west-central Caribbean Sea, between Cuba and the Yucatan Peninsula. Little Cayman Island (LCI) is relatively underdeveloped and understudied in comparison to its sister islands, Grand Cayman and Cayman Brac, and hosts less than 200 permanent residents over a 30 square kilometer area. However, like its sister islands, LCI is a small carbonate platform derived from reef building during the Oligocene, Miocene, and Quaternary. The shared geologic history of the Cayman Islands along with minimal human disturbance makes LCI an ideal site to study an island karst landscape. Conduction of field surveys, stratigraphic and petrologic comparisons between primary lithologic formations, and compilation of a geospatial inventory of karst features and lithology of LCI using GIS revealed novel insights into landscape evolution on LCI. In addition to surface karst surveys, several caves on the island were mapped. Cave morphologies suggest that evolution of LCI karst features have been driven by both hydroclimate, as well as salt and freshwater mixing, modulated by sea level fluctuations. These findings are mirrored in the lithology of partially dolomitized Miocene carbonates, which contain paleo-karst fill features and reveal hydroclimate influence, as well as enhanced resistance to dissolution in the present day, ostensibly from submersion in Mg-rich sea waters prior to the Quaternary. These findings shed light on the complex relationship of climate, geology, and karst landscape development on this particular carbonate island. This information is critical in anticipating structural and hydrogeological integrity on LCI under future climate change scenarios and serves as an example of the interplay linking climate and geologic processes to karst landscape development on small carbonate islands.

Quantitative collision induced mass spectrometry of substituted piperazines - A correlative analysis between theory and experiment

NASA Astrophysics Data System (ADS)

Ivanova, Bojidarka; Spiteller, Michael

2017-12-01

The present paper deals with quantitative kinetics and thermodynamics of collision induced dissociation (CID) reactions of piperazines under different experimental conditions together with a systematic description of effect of counter-ions on common MS fragment reactions of piperazines; and intra-molecular effect of quaternary cyclization of substituted piperazines yielding to quaternary salts. There are discussed quantitative model equations of rate constants as well as free Gibbs energies of series of m-independent CID fragment processes in GP, which have been evidenced experimentally. Both kinetic and thermodynamic parameters are also predicted by computational density functional theory (DFT) and ab initio both static and dynamic methods. The paper examines validity of Maxwell-Boltzmann distribution to non-Boltzmann CID processes in quantitatively as well. The experiments conducted within the latter framework yield to an excellent correspondence with theoretical quantum chemical modeling. The important property of presented model equations of reaction kinetics is the applicability in predicting unknown and assigning of known mass spectrometric (MS) patterns. The nature of "GP" continuum of CID-MS coupled scheme of measurements with electrospray ionization (ESI) source is discussed, performing parallel computations in gas-phase (GP) and polar continuum at different temperatures and ionic strengths. The effect of pressure is presented. The study contributes significantly to methodological and phenomenological developments of CID-MS and its analytical implementations for quantitative and structural analyses. It also demonstrates great prospective of a complementary application of experimental CID-MS and computational quantum chemistry studying chemical reactivity, among others. To a considerable extend this work underlies the place of computational quantum chemistry to the field of experimental analytical chemistry in particular highlighting the structural analysis.

THE EFFECT OF ALKYL AMINE TYPE ON THE EXTRACTION OF NITRIC ACID AND NITROSYLRUTHENIUM NITRATO COMPLEXES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Timmins, T.H.; Mason, E.A.

1963-04-01

An investigation of the solvent extraction characteristics of nitric acid and the nitrato complexes of nitrosylruthenium was conducted, using alkyl amines as extractants. The alkyl amines used were a primary amine Primene JMT, a tertiary amine trilaurylamine (TLA), and a quaternary amine Aliquat 336. The organic phase concentrations of HNO/sub 3/ resulting during extraction by alkyl amines were found to correlate well on the basis of the undissociated aqueous HNO/ sub 3/ activity for both salted (NaNO/sub 3/) and unsalted aqueous phases. The distribution ratios for Ru extraction showed better correlation on this basis than on the basis of aqueousmore » phase nitrate and nitric acid. The order of decreasing Ru extraction at low HNO/sub 3/ concentration (2N) was found to be Aliquat 336, TLA, and Primene JMT. At high HNO/sub 3/ concentration (9N). Primene JMT had the highest Ru extractability. Hapid dilution experiments were utilized to determine the number and aqueous phase concentrations of the extractable species of Ru, and the amine partition coefficients for the species. It was found that two Ru species are extractable, and the more extractable species is present in the aqueous phase at lower concentration than the less extractable species. The mole fractions of both species were found to increase with increasing HNO/sub 3/ concentration. The TLA partition coefficients for the extractable species were found to decrease with increasing HNO/sub 3/ concentration. The quaternary amine, Aliquat 336, was found to have partition coefficients an order of magnitude greater than the tertiary amine, TLA. Equations for the mole fractions and TLA partition coefficients in the region of HNO/sub 3/ concentration investigated were developed. (auth)« less

Observation of the noncovalent assembly and disassembly pathways of the chaperone complex MtGimC by mass spectrometry

PubMed Central

Fändrich, Marcus; Tito, Mark A.; Leroux, Michel R.; Rostom, Adam A.; Hartl, F. Ulrich; Dobson, Christopher M.; Robinson, Carol V.

2000-01-01

We have analyzed a newly described archaeal GimC/prefoldin homologue, termed MtGimC, by using nanoflow electrospray coupled with time-of-flight MS. The molecular weight of the complex from Methanobacterium thermoautotrophicum corresponds to a well-defined hexamer of two α subunits and four β subunits. Dissociation of the complex within the gas phase reveals a quaternary arrangement of two central subunits, both α, and four peripheral β subunits. By constructing a thermally controlled nanoflow device, we have monitored the thermal stability of the complex by MS. The results of these experiments demonstrate that a significant proportion of the MtGimC hexamer remains intact under low-salt conditions at elevated temperatures. This finding is supported by data from CD spectroscopy, which show that at physiological salt concentrations, the complex remains stable at temperatures above 65°C. Mass spectrometric methods were developed to monitor in real time the assembly of the MtGimC hexamer from its component subunits. By using this methodology, the mass spectra recorded throughout the time course of the experiment showed the absence of any significantly populated intermediates, demonstrating that the assembly process is highly cooperative. Taken together, these data show that the complex is stable under the elevated temperatures that are appropriate for its hyperthermophile host and demonstrate that the assembly pathway leads exclusively to the hexamer, which is likely to be a structural unit in vivo. PMID:11087821

A closer look into deep eutectic solvents: exploring intermolecular interactions using solvatochromic probes.

PubMed

Florindo, C; McIntosh, A J S; Welton, T; Branco, L C; Marrucho, I M

2017-12-20

Deep eutectic solvents (DESs) constitute a new class of ionic solvents that has been developing at a fast pace in recent years. Since these solvents are commonly suggested as green alternatives to organic solvents, it is important to understand their physical properties. In particular, polarity plays an important role in solvation phenomena. In this work, the polarity of different families of DESs was studied through solvatochromic responses of UV-vis absorption probes. Kamlet-Taft α, β, π* and E T N parameters were evaluated using different solvatochromic probes, as 2,6-dichloro-4-(2,4,6-triphenyl-N-pyridino)-phenolate (Reichardt's betaine dye 33), 4-nitroaniline, and N,N-diethyl-4-nitroaniline for several families of DESs based on cholinium chloride, dl-menthol and a quaternary ammonium salt ([N 4444 ]Cl). In addition, a study to understand the difference in polarity properties between DESs and the corresponding ILs, namely ILs based on cholinium cation and carboxylic acids as anions ([Ch][Lev], [Ch][Gly] and [Ch][Mal]), was carried out. The chemical structure of the hydrogen bond acceptor (HBA) in a DES clearly controls the dipolarity/polarizability afforded by the DES. Moreover, Kamlet-Taft parameters do not vary much within the family, but they differ among families based on different HBA, either for DESs containing salts ([Ch]Cl or [N 4444 ]Cl) or neutral compounds (dl-menthol). A substitution of the HBD was also found to play an important role in solvatochromic probe behaviour for all the studied systems.

Drainage lineaments in late Quaternary sediments, Ascension and East Baton Rouge Parishes, Louisiana

DOE Office of Scientific and Technical Information (OSTI.GOV)

Birdseye, R.U.; Christians, G.L.; Olson, J.L.

1988-09-01

Analysis of conventional aerial photographs, NHAP imagery, and topographic maps covering Ascension and East Baton Rouge Parishes in southeastern Louisiana reveals fine-textured parallel sets of drainage lineaments and numerous fluvial anomalies. Linear physiographic features include stream channels, natural levees, stream valleys, rectangular drainage patterns, and terrace scarps. Late Pleistocene and Holocene surfaces are involved, but only small drainages are affected and no such control is exerted on the Mississippi river. Most lineaments show preferred northeast and northwest trends. Orientations of mapped joint systems are similar to lineament orientations, which suggests that trends of physiographic lineaments are controlled by underlying structure.more » Several surface faults are mapped in the northern portion of the region, all of which strike essentially east-west. Salt domes are located in the subsurface to the south; however, they have no geomorphic expression and do not seem to be associated with the lineaments. Therefore, joints rather than faults or salt diapirs are a likely structural control. Joints may provide paths of weakness along which surface drainage might develop preferentially. Thus, joints probably exert an important control on the geomorphology of the region. The joint pattern appears to be related to the local distribution of the Mesozoic and Cenozoic strata, and may result from regional subsidence due to the thick accumulation of deltaic sediments. Conclusive subsurface data are currently unavailable, and shallow seismic surveys in the future may strengthen the case for an interpretation of structural control of drainage.« less

The gelation influence on diffusion and conductivity enhancement effect in renewable ionic gels based on a LMWG.

PubMed

Bielejewski, M; Rachocki, A; Kaszyńska, J; Tritt-Goc, J

2018-02-21

This paper reports the interdisciplinary study on molecular dynamics, ionic interactions and electrical conductivity in a quaternary ammonium salt (TMABr) ionogel based on a low molecular weight gelator (LMWG) in a wide range of electrolyte molar concentrations. The thermal scanning conductometry (TSC) was used to investigate the electric properties of the ionogels. The prepared TMABr/H 2 O/LMWG ionogel exhibits better ion transport properties than the dissociated TMA + cation in solution. The enhanced ionic conductivity effect (EICE) was observed in the concentration range of the TMABr salt up to 1 M. To investigate the transport properties of the TMA + cation and solvent molecules in the gel and sol phase, the NMR diffusiometry method was used. The field-cycling relaxometry method (FFC NMR) was applied to study the local motions of the electrolyte at the surface of the gelator matrix. On the basis of the obtained data, the higher ionic conductivity observed in the gel phase has been related to the microstructure of the gel matrix. The possible explanation for the origin of this effect has been given. The investigated system is a thermally reversible physical gel, all registered data were reproducible upon transforming the sample from gel to sol and back to the gel state, confirming the enhancement effect as a permanent property of the investigated ionogels. Therefore, the EICE has been proposed to be used as an internal sensor to monitor the condition of the ionogel phase, thus making them smart materials.

Thermodynamic Investigation of the Eutectic Mixture of the LiNO3-NaNO3-KNO3-Ca(NO3)2 System

NASA Astrophysics Data System (ADS)

Peng, Qiang; Ding, Jing; Wei, Xiaolan; Jiang, Gan

2017-09-01

Molten nitrate salt is usually employed as heat transfer or energy storage medium in concentrating solar power systems to improve the overall efficiency of thermoelectric conversion. In the present work, the liquidus curves of the LiNO3-NaNO3-KNO3-Ca(NO3)2 system is determined by conformal ionic solution theory according to the solid-liquid equilibrium state of the binary mixture. The calculated eutectic temperature of the mixture is 93.17 {°}C, which is close to the experimental value of 93.22 {°}C obtained from differential scanning calorimetry (DSC). Visualization observation experiments reveal that the quaternary eutectic mixture begins to partially melt when the temperature reaches 50 {°}C, and the degree of melting increases with temperature. The mixture is completely melted at 130 {°}C. The observed changes in the dissolved state at different temperatures correlate well with the DSC heat flow curve fluctuations.

Lubrication studies of some type III deep eutectic solvents (DESs)

NASA Astrophysics Data System (ADS)

Ahmed, Essa. I.; Abbott, Andrew. P.; Ryder, Karl S.

2017-09-01

It has previously been shown that eutectic mixtures of quaternary ammonium salts and hydrogen bond donors form liquids with properties similar to ionic liquids [1; 2]. These so-called deep eutectic solvents (DESs) have been shown to have physical properties which would make them useful as base lubricants. The base lubricant needs to show specific properties, including high viscosity index (VI), low friction coefficient (μ), low pour point and corrosivity. To determine the applicability of DESs as base lubricants, physical properties, corrosion and lubrication properties for four type III DESs have been studied and the results have been compared with mineral base oil. The data show that the lubrication properties of DESs are superior to mineral base oil for short distances. All DESs assessed here have higher VI (191, 147, 121 for Ethaline, Glyceline and Reline respectively compared with 100 for mineral base oil), lower pour points than mineral base oil and most of the liquids studied have shown very low corrosion rates (< 3 µm year-1 for mild steel).

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.

PubMed

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.

Enhancing cellulose accessibility of corn stover by deep eutectic solvent pretreatment for butanol fermentation.

PubMed

Xu, Guo-Chao; Ding, Ji-Cai; Han, Rui-Zhi; Dong, Jin-Jun; Ni, Ye

2016-03-01

In this study, an effective corn stover (CS) pretreatment method was developed for biobutanol fermentation. Deep eutectic solvents (DESs), consisted of quaternary ammonium salts and hydrogen donors, display similar properties to room temperature ionic liquid. Seven DESs with different hydrogen donors were facilely synthesized. Choline chloride:formic acid (ChCl:formic acid), an acidic DES, displayed excellent performance in the pretreatment of corn stover by removal of hemicellulose and lignin as confirmed by SEM, FTIR and XRD analysis. After optimization, glucose released from pretreated CS reached 17.0 g L(-1) and yield of 99%. The CS hydrolysate was successfully utilized in butanol fermentation by Clostridium saccharobutylicum DSM 13864, achieving butanol titer of 5.63 g L(-1) with a yield of 0.17 g g(-1) total sugar and productivity of 0.12 g L(-1)h(-1). This study demonstrates DES could be used as a promising and biocompatible pretreatment method for the conversion of lignocellulosic biomass into biofuel. Copyright © 2015 Elsevier Ltd. All rights reserved.

Study on the interaction between hematoporphyrin monomethyl ether and DNA and the determination of hematoporphyrin monomethyl ether using the resonance light scattering technique

NASA Astrophysics Data System (ADS)

Chen, Zhanguang; Song, Tianhe; Chen, Xi; Wang, Shaobin; Chen, Junhui

2010-10-01

The interaction between photosensitizer anticancer drug hematoporphyrin monomethyl ether (HMME) and ctDNA has been studied based on the decreased resonance light scattering (RLS) phenomenon. The RLS, UV-vis and fluorescence spectra characteristics of the HMME-ctDNA system were investigated. Besides, the phosphodiesters quaternary ammonium salt (PQAS), a kind of new gemini surfactant synthesized recently, was used to determine anticancer drug HMME based on the increasing RLS intensity. Under the optimum assay conditions, the enhanced RLS intensity was proportional to the concentration of HMME. The linear range was 0.8-8.4 μg mL -1, with correlation coefficient R2 = 0.9913. The detection limit was 0.014 μg mL -1. The human serum samples and urine samples were determined satisfactorily, which proved that this method was reliable and applicable in the determination of HMME in body fluid. The presented method was simple, sensitive and straightforward and could be a significant method in clinical analysis.

Synthesis of quaternary chalcogenide CZTS nanoparticles by a hydrothermal route

NASA Astrophysics Data System (ADS)

Das, S.; Sa, K.; Mahakul, P. C.; Raiguru, J.; Alam, I.; Subramanyam, BVRS; Mahanandia, P.

2018-03-01

Cu2ZnSnS4 (CZTS) has emerged as a potential absorber towards inorganic photovoltaic device application for its outstanding properties like non toxicity, earth abundancy nature, optimal band gap matched with solar spectrum (1.45- 1.65eV), high absorption coefficient (104cm‑1). Here, a low cost, environment friendly facile hydrothermal route to synthesize phase pure CZTS nanoparticles using Cu (II), Zn (II), Sn (II) inorganic metal salts and thiourea as Sulphur source in distilled water solution as precursor is reported. The as synthesized samples characterized by X-Ray diffraction (XRD) and RAMAN confirmed structure and phase of CZTS nanocrystals. The morphology of the prepared CZTS have been characterized by scanning electron microscopy (SEM). The particle size is found in the range 4-5 nm with crystalline nature have been characterized by transmission electron microscope (TEM). The optical band gap of the as prepared samples is calculated to be 1.65eV from UV-Visible analysis which proves it can be used towards photovoltaic applications.

Optically active antifungal azoles. XII. Synthesis and antifungal activity of the water-soluble prodrugs of 1-[(1R,2R)-2-(2,4-difluorophenyl)-2-hydroxy-1-methyl-3-(1H-1,2,4-triazol-1-yl)propyl]-3-[4-(1H-1-tetrazolyl)phenyl]-2-imidazolidinone.

PubMed

Ichikawa, T; Kitazaki, T; Matsushita, Y; Yamada, M; Hayashi, R; Yamaguchi, M; Kiyota, Y; Okonogi, K; Itoh, K

2001-09-01

1-[(1R,2R)-2-(2,4-Difluorophenyl)-2-hydroxy-1-methyl-3-(1H-1,2,4-triazol-1-yl)propyl]-3-[4-(1H-1-tetrazolyl)phenyl]-2-imidazolidinone (1: TAK-456) was selected as a candidate for clinical trials, but since its water-solubility was insufficient for an injectable formulation, the quaternary triazolium salts 2 were designed as water-soluble prodrugs. Among the prodrugs prepared, 4-acetoxymethyl-1-[(2R,3R)-2-(2,4-difluorophenyl)-2-hydroxy-3-[2-oxo-3-[4-(1H-1-terazolyl)phenyl]-1-imidazolidinyl]butyl]-1H-1,2,4-triazolium chloride (2a: TAK-457) was selected as an injectable candidate for clinical trials based on the results of evaluations on solubility, stability, hemolytic effect and in vivo antifungal activities.

Synthesis and characterization of chitosan quaternary ammonium salt and its application as drug carrier for ribavirin.

PubMed

Li, Si-Dong; Li, Pu-Wang; Yang, Zi-Ming; Peng, Zheng; Quan, Wei-Yan; Yang, Xi-Hong; Yang, Lei; Dong, Jing-Jing

2014-11-01

N-(2-hydroxyl) propyl-3-trimethyl ammonium chitosan chloride (HTCC) is hydro-soluble chitosan (CS) derivative, which can be obtained by the reaction between epoxypropyl trimethyl ammonium chloride (ETA) and CS. The preparation parameters for the synthesis of HTCC were optimized by orthogonal experimental design. ETA was successfully grafted into the free amino group of CS. Grafting of ETA with CS had great effect on the crystal structure of HTCC, which was confirmed by the XRD results. HTCC displayed higher capability to form nanoparticles by crosslinking with negatively charged sodium tripolyphosphate (TPP). Ribavrin- (RIV-) loaded HTCC nanoparticles were positively charged and were spherical in shape with average particle size of 200 nm. More efficient drug encapsulation efficiency and loading capacity were obtained for HTCC in comparison with CS, however, HTCC nanoparticles displayed faster release rate due to its hydro-soluble properties. The results suggest that HTCC is a promising CS derivative for the encapsulation of hydrophilic drugs in obtaining sustained release of drugs.

Radiocarbon analysis of halophilic microbial lipids from an Australian salt lake

NASA Astrophysics Data System (ADS)

Bray, P. Sargent; Jones, Claudia M.; Fallon, Stewart J.; Brocks, Jochen J.; George, Simon C.

2012-01-01

Assigning accurate dates to hypersaline sediments opens important terrestrial records of local and regional paleoecologies and paleoclimatology. However, as of yet no conventional method of dating hypersaline systems has been widely adopted. Biomarker, mineralogical, and radiocarbon analyses of sediments and organic extracts from a shallow (13 cm) core from a hypersaline playa, Lake Tyrrell, southeastern Australia, produce a coherent age-depth curve beginning with modern microbial mats and extending to ~ 7500 cal yr BP. These analyses are furthermore used to identify and constrain the timing of the most recent change in hydrological regime at Lake Tyrrell, a shift from a clay deposit to the precipitation of evaporitic sands occurring at some time between ~ 4500 and 7000 yr. These analyses show the potential for widespread dating of hypersaline systems integrating the biomarker approach, reinforce the value of the radiocarbon content of biomarkers in understanding the flow of carbon in modern ecologies, and validate the temporal dimension of data provided by biomarkers when dating late Quaternary sediments.

Recent Progress on the Stereoselective Synthesis of Cyclic Quaternary α-Amino Acids

PubMed Central

Cativiela, Carlos; Ordóñez, Mario

2010-01-01

The most recent papers describing the stereoselective synthesis of cyclic quaternary α-amino acids are collected in this review. The diverse synthetic approaches are classified according to the size of the ring and taking into account the bond that is formed to complete the quaternary skeleton. PMID:20300486

The ichthyofauna of limnic systems in Quaternary deposits of extreme southern Brazil

PubMed Central

Assumpção, Cindy M.; Quintela, Fernando M.; Corrêa, Fabiano; Loebmann, Daniel

2016-01-01

Abstract The Quaternary in the state of Rio Grande do Sul (RS), southern Brazil, is geologically represented by the coastal plain and was originated by successive events of Pleistocene-Holocene marine transgressions and the occurrence of alluvial deposits. This paper aimed to characterize the fish assemblage occurring in a swampy Quaternary area adjacent to Lagoa Pequena, a lacustrine system connected to the west margin of the Laguna dos Patos estuary. A checklist is also provided of the ichthyofauna so far recorded in limnic systems of Quaternary deposits in the state of Rio Grande do Sul. A total of 42 species was recorded, distributed in nine orders, 18 families and 31 genera. Characidae and Cichlidae were the most representative families, comprising 15 and 4 species respectively. A bibliographic revision associated to our sample data revealed the occurrence of 156 species in limnic systems inserted in RS Quaternary deposits (114 limnic, 15 marine/estuarine/limnic, ten marine/estuarine, nine estuarine/limnic and eight marine). Characiformes and Siluriformes are the most diverse orders, corroborating the Neotropical pattern. Seven species can be considered endemic to RS Quaternary deposits. PMID:28174498

Analysis of multiple quaternary ammonium compounds in the brain using tandem capillary column separation and high resolution mass spectrometric detection.

PubMed

Falasca, Sara; Petruzziello, Filomena; Kretz, Robert; Rainer, Gregor; Zhang, Xiaozhe

2012-06-08

Endogenous quaternary ammonium compounds are involved in various physiological processes in the central nervous system. In the present study, eleven quaternary ammonium compounds, including acetylcholine, choline, carnitine, acetylcarnitine and seven other acylcarnitines of low polarity, were analyzed from brain extracts using a two dimension capillary liquid chromatography-Fourier transform mass spectrometry method. To deal with their large difference in hydrophobicities, tandem coupling between reversed phase and hydrophilic interaction chromatography columns was used to separate all the targeted quaternary ammonium compounds. Using high accuracy mass spectrometry in selected ion monitoring mode, all the compounds could be detected from each brain sample with high selectivity. The developed method was applied for the relative quantification of these quaternary ammonium compounds in three different brain regions of tree shrews: prefrontal cortex, striatum, and hippocampus. The comparative analysis showed that quaternary ammonium compounds were differentially distributed across the three brain areas. The analytical method proved to be highly sensitive and reliable for simultaneous determination of all the targeted analytes from brain samples. Copyright © 2012 Elsevier B.V. All rights reserved.

Preparation and testing of quaternized chitosan nanoparticles as gene delivery vehicles.

PubMed

Li, Guang-Feng; Wang, Jing-Cheng; Feng, Xin-Min; Liu, Zhen-Dong; Jiang, Chao-Yong; Yang, Jian-Dong

2015-04-01

The aim of this study was to synthesize a chitosan (CS) derivative, a quaternary ammonium salt crystal called N-2-hydroxypropyl trimethyl ammonium chloride chitosan (HACC), and test a series of HACC and pEGFP-DNA complexes at different weight ratios for their efficiency of gene delivery into human cells. CS was modified with cationic etherifying agent to obtain the CS derivative. Fourier transform infrared spectra were recorded on KBr pellets with a spectrometer. (1)H nuclear magnetic resonance (NMR) spectra of HACC were obtained using a spectrometer. HACC was subsequently used to prepare HACC/DNA complexes at different weight ratios by coacervation method. The resulting particle size and surface charge were assessed by laser light scattering using a zeta potential analyzer. The HACC/DNA complex formation and DNA protection in the nanoparticle complex was investigated by gel mobility shift assay and DNase I protection assay, respectively. The cytotoxicity of HACC and HACC/DNA nanoparticles was evaluated by MTT assay using (mesenchymal stem cell) MSC lines. The nanoscale structure of the particles was obtained by transmission electron microscope (TEM). The FTIR spectrum of HACC showed the characteristic quaternary ammonium group absorption band at 1475 cm(-1), which indicated the presence of quaternary ammonium group. The successful synthesis of HACC was also confirmed by (1)H NMR spectrum. HACC showed good solubility in water and was electropositive. HACC efficiently packed and protected pEGFP-DNA at a weight ratio of 10. With increased weight ratios, the surface charge of the composite particle increased from negative to positive, the average particle size increased, and HACC nanoparticle had a higher carrying efficiency. The nanoparticles released DNA in two distinct phases, and 55 % was released within the first 20 h of solubilization. The nanoparticles under TEM showed circular or oval shapes. The particles exhibited no cytotoxicity against human cells. No significant difference in gene delivery efficiency was detected between HACC/pEGFP-GDNF and liposome/pEGFP-GDNF complexes (33.8 vs. 34 %, P = 0.363). In this study, HACC was successfully synthesized, and HACC/DNA complex assembled efficiently. HACC showed strong DNA binding affinity and high protection of DNA and was non-cytotoxic to human cells. The particles had appropriate nanostructure, mean diameter, and DNA release time. The results suggest that HACC nanoparticles are a novel tool for efficient and safe gene delivery.

Origin and late quaternary tectonism of a western Canadian continental shelf trough

NASA Astrophysics Data System (ADS)

Moslow, Thomas F.; Luternauer, John L.; Rohr, Kristin

1991-08-01

Analyses of high resolution and multi-channel seismic profiles from the central continental shelf of western Canada ascribe a late Quaternary glacial origin to large-scale troughs. Along the margins of Moresby Trough, one of three large-scale cross-shelf bathymetric depressions in Queen Charlotte Sound, seismic profiles within Quaternary sediments show a divergence of reflectors, thickening and folding of seismic units, and concavity of reflectors suggestive of drag. Compactional subsidence, growth faulting, and compaction faulting are also observed. Fault traces commonly terminate below the seabed. Deformation of Quaternary sediments due to faulting is plastic in nature and maximum offset of reflectors is 2.5 m. The observed Quaternary deformation appears to be a product of rapid deposition, loading and subsidence of late Quaternary sediment, which is unrelated to seismic activity. In addition, Quaternary faulting was probably activated by post-glacial loading and isostatic rebound of consolidated Tertiary strata along the margins of continental shelf troughs. The presence of mass movement (slump or debris flow) deposits overlying lithified Tertiary strata along the flanks of Moresby Trough provides the only evidence of seismic activity in the study area. The lack of a mud drape over these deposits implies a late Holocene age for the timing of their emplacement. The Quaternary troughs are incised into Tertiary-aged sedimentary fill of the Queen Charlotte basin. Previous workers had interpreted seafloor escarpments paralleling the trough margins to indicate that the location of Moresby Trough was controlled by renewed or continued activity on Tertiary-aged faults. A multi-channel seismic line across Moresby Trough shows that such an escarpment on the seafloor does not correlate to faults either in the Tertiary basin fill or the underlying basement. Tertiary reflectors are continuous underneath Moresby Trough; the seafloor escarpment is an erosional feature and was not created by reactivation of Tertiary structures. Trough erosion and subsequent fill (up to 175 m thick) are entirely of Quaternary age.

Efficiency improvement of green light-emitting diodes by employing all-quaternary active region and electron-blocking layer

NASA Astrophysics Data System (ADS)

Usman, Muhammad; Saba, Kiran; Han, Dong-Pyo; Muhammad, Nazeer

2018-01-01

High efficiency of green GaAlInN-based light-emitting diode (LED) has been proposed with peak emission wavelength of ∼510 nm. By introducing quaternary quantum well (QW) along with the quaternary barrier (QB) and quaternary electron blocking layer (EBL) in a single structure, an efficiency droop reduction of up to 29% has been achieved in comparison to the conventional GaN-based LED. The proposed structure has significantly reduced electrostatic field in the active region. As a result, carrier leakage has been minimized and spontaneous emission rate has been doubled.

Quaternary complexes composed of plasmid DNA/protamine/fish sperm DNA/stearic acid grafted chitosan oligosaccharide micelles for gene delivery.

PubMed

Du, Yong-Zhong; Lu, Ping; Yuan, Hong; Zhou, Jian-Ping; Hu, Fu-Qiang

2011-01-01

Quaternary complexes with condensed core of plasmid DNA, protamine, fish sperm DNA and shell of stearic acid grafted chitosan oligosaccharide (CSO-SA), were prepared. The CSO-SA could self-assemble to form nano-sized micelles in aqueous solution and demonstrated excellent internalization ability of tumor cells. Dynamic light scattering (DLS) measurement and transmission electrostatic microscope (TEM) images showed that quaternary complexes had spherical shape with about 25 nm number average diameter, and the size of quaternary complexes was smaller than that of CSO-SA micelles and CSO-SA micelles/plasmid DNA binary complexes. The transfection efficiencies of quaternary complexes on HEK293 and MCF-7 cells increased with incubation time, and were significantly higher than that of CSO-SA micelles/plasmid DNA binary complexes. The optimal transfection efficiency of quaternary complexes on HEK293 and MCF-7 cells measured by flow cytometer after 96 h was 23.82% and 41.43%, respectively. Whereas, the transfection efficiency of Lipofectamine™ 2000 on HEK293 and MCF-7 cells after 96 h was 32.45% and 33.23%, respectively. The data of luciferease activity measurement showed that the optimal ratio of plasmid DNA:fish sperm DNA:protamine:CSO-SA was 1:1:5:5. The results indicated that the present quaternary complexes were potential non-viral gene delivery system. Copyright © 2010 Elsevier B.V. All rights reserved.

Using Paleoseismic Trenching and LiDAR Analysis to Evaluate Rupture Propagation Through Segment Boundaries of the Central Wasatch Fault Zone, Utah

NASA Astrophysics Data System (ADS)

Bennett, S. E. K.; DuRoss, C. B.; Reitman, N. G.; Devore, J. R.; Hiscock, A.; Gold, R. D.; Briggs, R. W.; Personius, S. F.

2014-12-01

Paleoseismic data near fault segment boundaries constrain the extent of past surface ruptures and the persistence of rupture termination at segment boundaries. Paleoseismic evidence for large (M≥7.0) earthquakes on the central Holocene-active fault segments of the 350-km-long Wasatch fault zone (WFZ) generally supports single-segment ruptures but also permits multi-segment rupture scenarios. The extent and frequency of ruptures that span segment boundaries remains poorly known, adding uncertainty to seismic hazard models for this populated region of Utah. To address these uncertainties we conducted four paleoseismic investigations near the Salt Lake City-Provo and Provo-Nephi segment boundaries of the WFZ. We examined an exposure of the WFZ at Maple Canyon (Woodland Hills, UT) and excavated the Flat Canyon trench (Salem, UT), 7 and 11 km, respectively, from the southern tip of the Provo segment. We document evidence for at least five earthquakes at Maple Canyon and four to seven earthquakes that post-date mid-Holocene fan deposits at Flat Canyon. These earthquake chronologies will be compared to seven earthquakes observed in previous trenches on the northern Nephi segment to assess rupture correlation across the Provo-Nephi segment boundary. To assess rupture correlation across the Salt Lake City-Provo segment boundary we excavated the Alpine trench (Alpine, UT), 1 km from the northern tip of the Provo segment, and the Corner Canyon trench (Draper, UT) 1 km from the southern tip of the Salt Lake City segment. We document evidence for six earthquakes at both sites. Ongoing geochronologic analysis (14C, optically stimulated luminescence) will constrain earthquake chronologies and help identify through-going ruptures across these segment boundaries. Analysis of new high-resolution (0.5m) airborne LiDAR along the entire WFZ will quantify latest Quaternary displacements and slip rates and document spatial and temporal slip patterns near fault segment boundaries.

Polarized Infrared Reflectance Studies of Quaternary In0.04Al0.06Ga0.90N

NASA Astrophysics Data System (ADS)

Bakhori, S. K. Mohd; Lee, S. C.; Ahmad, M. A.; Ng, S. S.; Hassan, H. Abu

2010-07-01

Group III-nitride has re-gained considerable interest recently as wide direct band gap semiconductor materials for opto-electronic and high power devices. The quaternary InAlGaN have great flexibility in tailoring their band gap profile while maintaining their lattice-matching and structural integrity. In this study, we report for the first time the polarized infrared (IR) reflectance studies of quaternary In0.04Al0.06Ga0.90N by using Fourier transform infrared spectroscopy of Perkin-Elmer. The quaternary In0.04Al0.06Ga0.90N epilayers was grown on sapphire by molecular beam epitaxy. The polarized IR reflectance spectra obtained at incident angle of 15° were then compared with modeling spectrum of damped harmonic oscillator. Through this study, the transverse and longitudinal optical phonon modes of quaternary In0.04Al0.06Ga0.90N epilayers were obtained.

Thermally Reduced Graphene Oxide Electrochemically Activated by Bis-Spiro Quaternary Alkyl Ammonium for Capacitors.

PubMed

He, Tieshi; Meng, Xiangling; Nie, Junping; Tong, Yujin; Cai, Kedi

2016-06-08

Thermally reduced graphene oxide (RGO) electrochemically activated by a quaternary alkyl ammonium-based organic electrolytes/activated carbon (AC) electrode asymmetric capacitor is proposed. The electrochemical activation process includes adsorption of anions into the pores of AC in the positive electrode and the interlayer intercalation of cations into RGO in the negative electrode under high potential (4.0 V). The EA process of RGO by quaternary alkyl ammonium was investigated by X-ray diffraction and electrochemical measurements, and the effects of cation size and structure were extensively evaluated. Intercalation by quaternary alkyl ammonium demonstrates a small degree of expansion of the whole crystal lattice (d002) and a large degree of expansion of the partial crystal lattice (d002) of RGO. RGO electrochemically activated by bis-spiro quaternary alkyl ammonium in propylene carbonate/AC asymmetric capacitor exhibits good activated efficiency, high specific capacity, and stable cyclability.

Multi-valued logic gates based on ballistic transport in quantum point contacts.

PubMed

Seo, M; Hong, C; Lee, S-Y; Choi, H K; Kim, N; Chung, Y; Umansky, V; Mahalu, D

2014-01-22

Multi-valued logic gates, which can handle quaternary numbers as inputs, are developed by exploiting the ballistic transport properties of quantum point contacts in series. The principle of a logic gate that finds the minimum of two quaternary number inputs is demonstrated. The device is scalable to allow multiple inputs, which makes it possible to find the minimum of multiple inputs in a single gate operation. Also, the principle of a half-adder for quaternary number inputs is demonstrated. First, an adder that adds up two quaternary numbers and outputs the sum of inputs is demonstrated. Second, a device to express the sum of the adder into two quaternary digits [Carry (first digit) and Sum (second digit)] is demonstrated. All the logic gates presented in this paper can in principle be extended to allow decimal number inputs with high quality QPCs.

Stratigraphic evolution of the inner continental shelf in response to late Quaternary relative sea-level change, northwestern Gulf of Maine

USGS Publications Warehouse

Barnhardt, W.A.; Belknap, D.F.; Kelley, J.T.

1997-01-01

Accumulations of deltaic and littoral sediments on the inner continental shelf of Maine, Gulf of Maine, preserve a record of postglacial sea-level changes and shoreline migrations. The depositional response of coastal environments to a cycle of regression, lowstand, and transgression was examined with seismic-reflection profiles, vibracores, and radiocarbon dates collected from sediments at the mouths of the Kennebec and Penobscot Rivers. Sequence-stratigraphie analysis of these data reveals two distinctly different successions of late Quaternary deposits that represent end members in an evolutionary model for this glaciated coast. Seaward of the Kennebec River, coarsegrained shorelines with foreset beds occur at depths of 20-60 m and outline the lobate margin of the Kennebec River paleodelta, a complex, rock-framed accumulation of glaciomarine and deltaic sediments capped by estuarine and marine deposits. Sand derived from this system today supports large barrier spits and extensive salt marshes. In contrast, the mouth of the Penobscot River is characterized by thick deposits of glaciomarine mud overlain by marine mud of Holocene age, including gas-charged zones that have locally evolved into fields of pockmarks. The distinct lack of sand and gravel seaward of the Penobscot River and its abundance seaward of the Kennebec River probably reflect differences in sediment sources and the physiography of the two watersheds. The contrasting stratigraphie framework of these systems demonstrates the importance of understanding local and regional differences in sediment supply, sea-level change, bedrock structure, and exposure to waves and tides in order to model river-mouth deposition on glaciated coasts. Evolution of shelf deposits was largely controlled by relative sea level, which locally fell from a highstand (+60 to +70 m at 14 ka) contemporary with deglaciation to a lowstand (-55 m at 10.8 ka). The sea-level lowering was accompanied by fluvial incision of older deposits, producing a regressive, basal unconformity. Major rivers deposited abundant sediment over this surface. Sea level then rose at varying rates, extensively reworking formerly emergent parts of the shelf and producing a shoreface ravinement surface in areas exposed to waves. A tidal ravinement surface has developed in sheltered embayments where erosion is due mainly to tidal currents. Incised valleys in both settings preserve transgressive estuarine deposits that contain lagoonal bivalves and salt-marsh foraminifera at depths of 15-30 m. These deposits accumulated ca. 9.2-7.3 ka, locally a period of relatively slow sea-level rise.

Elaboration et caracterisation de nanocomposites polyethylene/montmorillonite

NASA Astrophysics Data System (ADS)

Stoeffler, Karen

This research project consists in preparing polyethylene/montmorillonite nanocomposites for film packaging applications. Montmorillonite is a natural clay with an exceptional aspect ratio. In recent years, its incorporation in polymer matrices has attracted great interest. The pioneer work from Toyota on polyamide-6/montmorillonite composites has shown that it was possible to disperse the clay at a nanometric scale. Such a structure, so-called exfoliated, leads to a significant increase in mechanical, barrier and fire retardant properties, even at low volumetric fractions of clay. This allows a valorization of the polymeric material at moderate cost. Due to its high polarity, montmorilloite exfoliation in polymeric matrices is problematic. In the particular case of polyolefin matrices, the platelets dispersion remains limited: most frequently, the composites obtained exhibit conventional structures (microcomposites) or intercalated structures. To solve this problem, two techniques are commonly employed: the surface treatment of the clay, which allows the expansion of the interfoliar gallery while increasing the affinity between the clay and the polymer, and the use of a polar compatibilizing agent (grafted polyolefin). The first part of this thesis deals with the preparation and the characterization of highly thermally stable organophilic montmorillonites. Commercial organophilic montmorillonites are treated with quaternary ammonium intercalating agents. However, those intercalating agents present a poor thermal stability and are susceptible to decompose upon processing, thus affecting the clay dispersion and the final properties of the nanocomposites. In this work, it was proposed to modify the clay with alkyl pyridinium, alkyl imidazolium and alkyl phosphonium intercalating agents, which are more stable than ammonium based cations. Organophilic montmorillonites with enhanced thermal stabilites compared to commercial organoclays (+20°C to +70°C) were prepared. The effect of the chemical structure of the intercalating agent on the capacity of the organoclay to be dispersed in polyethylene matrices was analyzed. In addition, the influence of the dispersion on the thermal stability of the nanocomposites prepared is discussed. In a second part, the effect of the compatibilizing agent characteristics on the quality of the clay dispersion in polyethylene/montmorillonite nanocomposites was analyzed. The mechanical properties and the oxygen permeability of the nanocomposites were evaluated and related to the level of clay delamination and to the strength of the polymer/clay interface, which was evaluated through surface tension measurements.

Use of carbon steel ball bearings to determine the effect of biocides and corrosion inhibitors on microbiologically influenced corrosion under flow conditions.

PubMed

Pinnock, Tijan; Voordouw, Johanna; Voordouw, Gerrit

2018-05-10

A consortium of sulfate-reducing bacteria consisting mostly of Desulfovibrio, Desulfomicrobium, and Desulfocurvus from oil field produced water was cultivated in a chemostat, receiving medium with 20 mM formate and 10 mM sulfate as the energy and 1 mM acetate as the carbon source. The chemostat effluent, containing 5 mM sulfide and 0.5 mM of residual acetate, was passed through 1-ml syringe columns with 60 carbon steel ball bearings (BBs) of 53.6 ± 0.1 mg each at a flow rate of 0.8 ml/h per column. These were treated every 5 days with 1.6 ml of 300 ppm of glutaraldehyde (Glut), tetrakis(hydroxymethyl)phosphonium sulfate (THPS), benzalkonium chloride (BAC), or Glut/BAC, a mixture of Glut and BAC. Alternatively, BBs were treated with 33% (v/v) of a water-soluble (CR_W) or an oil-soluble (CR_O1 or CR_O3) corrosion inhibitor for 20 s after which the corrosion inhibitor was drained off and BBs were packed into columns. The effluent of untreated control columns had no acetate. Treatment with the chemically reactive biocides Glut and THPS, as well as with Glut/BAC, gave a transient increase of acetate indicating decreased microbial activity. This was not seen with BAC alone indicating it to be the least effective biocide. Relative to untreated BBs (100%), those treated periodically with Glut, THPS, BAC, or Glut/BAC had a general weight loss corrosion rate of 91, 81, 45, and 36% of the untreated rate of 0.104 ± 0.004 mm/year, respectively. Single treatment with corrosion inhibitors decreased corrosion to 48, 2, and 1% of the untreated rate for CR_W, CR_O1 and CR_O3, respectively. Analysis of the distribution of corrosion rates from the weight loss of individual BBs (N = 120) indicated the presence of a more slowly and a more rapidly corroding group. BAC treatment prevented emergence of the latter, and this quaternary ammonium detergent appeared most effective in decreasing corrosion not because of its biocidal properties, but because of its corrosion inhibitory properties.

Deformation and Quaternary Faulting in Southeast Missouri across the Commerce Geophysical Lineament

USGS Publications Warehouse

Stephenson, W.J.; Odum, J.K.; Williams, R.A.; Pratt, T.L.; Harrison, R.W.; Hoffman, D.

1999-01-01

High-resolution seismic-reflection data acquired at three sites along the surface projection of the Commerce geophysical lineament in southeast Missouri reveal a complex history of post-Cretaceous faulting that has continued into the Quaternary. Near Qulin, Missouri, approximately 20 m of apparent vertical fault displacement has occurred in the Quaternary. Reflection data collected at Idalia Hill, about 45 km to the northeast, reveal a series of reverse and possibly right-lateral strike-slip faults with Quaternary displacement. In the Benton Hills, 45 km northeast of Idalia Hill, seismic data image a complicated series of anticlinal and synclinal fault-bounded blocks immediately north of the Commerce fault. We infer that most of the deformation imaged in the upper 400 m of these three data sets occurred since post-Cretaceous time, and a significant portion of it occurred during Quaternary time. Collectively, these seismic data along with geomorphic and surface-geologic evidence suggest (1) the existence of at least one potential seismogenic structure in southeastern Missouri outside the main zones of New Madrid seismicity, and (2) these structures have been active during the Quaternary. The geographic location of the imaged deformation suggests it is related to structures along with the Commerce geophysical lineament.

Quaternary extensional growth folding beneath Reno, Nevada, imaged by urban seismic profiling

USGS Publications Warehouse

Stephenson, William J.; Frary, Roxy N.; Louie, John; Odum, Jackson K.

2013-01-01

We characterize shallow subsurface faulting and basin structure along a transect through heavily urbanized Reno, Nevada, with high‐resolution seismic reflection imaging. The 6.8 km of P‐wave data image the subsurface to approximately 800 m depth and delineate two subbasins and basin uplift that are consistent with structure previously inferred from gravity modeling in this region of the northern Walker Lane. We interpret two primary faults that bound the uplift and deform Quaternary deposits. The dip of Quaternary and Tertiary strata in the western subbasin increases with greater depth to the east, suggesting recurrent fault motion across the westernmost of these faults. Deformation in the Quaternary section of the western subbasin is likely evidence of extensional growth folding at the edge of the Truckee River through Reno. This deformation is north of, and on trend with, previously mapped Quaternary fault strands of the Mt. Rose fault zone. In addition to corroborating the existence of previously inferred intrabasin structure, these data provide evidence for an active extensional Quaternary fault at a previously unknown location within the Truckee Meadows basin that furthers our understanding of both the seismotectonic framework and earthquake hazards in this urbanized region.

Evaluation of materials proposed for use in space flight

NASA Technical Reports Server (NTRS)

Duncan, W. C.

1981-01-01

The cutaneous primary irritancy and allergenicity potential of cotton shirts/fabrics treated with flame retardants were evaluated in order to establish their suitability for spacecraft crew use. Twenty-five volunteer human subjects were patch tested on the back utilizing standard methodology, with both treated and untreated cotton fabric. The fabric was treated with tetrakis (hydroxymethyl) phosphonium hydroxide and subsequently cured with gaseous ammonia. The final treatment comprised adding on dicyandiamine phosphoric acid. None of the individuals experienced primary irritant or allergic reactions attributable to the fabric during induction or challenge patch testing. Likewise, there were no reactions to treated or untreated fabric patches placed on ten subjects of the usage panel at the conclusion of the study.

Sequential character of low-energy ternary and quaternary nuclear fission

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kadmensky, S. G., E-mail: kadmensky@phys.vsu.ru; Bulychev, A. O.

2016-09-15

An analysis of low-energy true ternary (quaternary) nuclear fission leads to the conclusion that these fission modes have a sequential two-step (three-step) character such that the emission of a third particle (third and fourth particles) and the separation of fission fragments occur at distinctly different instants, in contrast to the simultaneous emergence of all fission products in the case of onestep ternary (quaternary) fission. This conclusion relies on the following arguments. First, the emission of a third particle (third and fourth particles) from a fissile nucleus is due to a nonevaporative mechanism associated with a nonadiabatic character of the collectivemore » deformation motion of this nucleus at the stages preceding its scission. Second, the axial symmetry of the deformed fissile compound nucleus and the direction of its symmetry axis both remain unchanged at all stages of ternary (quaternary) fission. This circumstancemakes it possible to explain themechanism of the appearance of observed anisotropies and T — odd asymmeries in the angular distributions of products of ternary (quaternary) nuclear fission. Third, the T —odd asymmetry discovered experimentally in ternary nuclear fission induced by cold polarized neutrons obeys the T —invariance condition only in the case of a sequential two-step (three-step) character of true ternary (quaternary) nuclear fission. At the same time, this asymmetry is not a T —invariant quantity in the case of the simultaneous emission of products of true ternary (quaternary) nuclear fission from the fissile compound nucleus.« less

Synthesis and Characterization of Perfluoro Quaternary Ammonium Anion Exchange Membranes

DTIC Science & Technology

2012-01-01

study, new alkaline exchange membranes were prepared from the perfluorinated 3M ionomer with various quaternary ammonium cations attached with...ammonium anion exchange membranes Report Title ABSTRACT In this study, new alkaline exchange membranes were prepared from the perfluorinated 3M ionomer...exchange membranes were prepared from the perfluorinated 3M ionomer with vari- ous quaternary ammonium cations attached with sulfonamide linkage. The

Self-Assembly of Helical Ribbons

DTIC Science & Technology

1999-07-01

detergent, a phosphatidylcholine or a fatty acid , and a steroid analog of cholesterol. In almost all systems, two different pitch types of helical...quater- nary sterol systems (QSS), on a quaternary fatty acid system (QFAS), and on two lipid concentrate systems, as defined below. In addition to high...lipid concentrate; QSS, quaternary sterol systems; QFAS, quaternary fatty acid system; NaTC, sodium taurocholate; DOPC, 1,2-dioleoyl-glycero- 3

Dynamic covalent chemistry enables formation of antimicrobial peptide quaternary assemblies in a completely abiotic manner

NASA Astrophysics Data System (ADS)

Reuther, James F.; Dees, Justine L.; Kolesnichenko, Igor V.; Hernandez, Erik T.; Ukraintsev, Dmitri V.; Guduru, Rusheel; Whiteley, Marvin; Anslyn, Eric V.

2018-01-01

Naturally occurring peptides and proteins often use dynamic disulfide bonds to impart defined tertiary/quaternary structures for the formation of binding pockets with uniform size and function. Although peptide synthesis and modification are well established, controlling quaternary structure formation remains a significant challenge. Here, we report the facile incorporation of aryl aldehyde and acyl hydrazide functionalities into peptide oligomers via solid-phase copper-catalysed azide-alkyne cycloaddition (SP-CuAAC) click reactions. When mixed, these complementary functional groups rapidly react in aqueous media at neutral pH to form peptide-peptide intermolecular macrocycles with highly tunable ring sizes. Moreover, sequence-specific figure-of-eight, dumbbell-shaped, zipper-like and multi-loop quaternary structures were formed selectively. Controlling the proportions of reacting peptides with mismatched numbers of complementary reactive groups results in the formation of higher-molecular-weight sequence-defined ladder polymers. This also amplified antimicrobial effectiveness in select cases. This strategy represents a general approach to the creation of complex abiotic peptide quaternary structures.

Viscosities of nonelectrolyte liquid mixtures. III. Selected binary and quaternary mixtures

NASA Astrophysics Data System (ADS)

Wakefield, D. L.

1988-05-01

This paper is the final in a series of three viscosity and density studies of pure n-alkanes and selected binary and quaternary mixtures. A standard U-tube viscometer was used for viscosity measurements, and a Pyrex flask-type pycnometer was used for density determinations. Results are given here for pure alkane and selected binary mixtures of n-tetradecane + n-octane, for selected quaternary mixtures of n-hexadecane + n-dodecane + n-decane + n-hexane, and for pure and selected quaternary mixtures of n-hexadecane + n-dodecane + n-nonane + n-heptane at 303.16 and 308.16 K. The principle of congruence was tested, as was the Grunberg and Nissan equation, as they have been shown to be useful as prediction techniques for other n-alkane binary mixtures. Comparisons were made between the two groups of quaternary alkane mixtures and the binary n-tetradecane + n-octane mixtures of the same “pseudo” composition to understand better the dependence of mixture viscosities on the composition parameter.

Poly(3,4-ethylenedioxythiophene)-Poly(styrenesulfonate) Interlayer Insertion Enables Organic Quaternary Memory.

PubMed

Cheng, Xue-Feng; Hou, Xiang; Qian, Wen-Hu; He, Jing-Hui; Xu, Qing-Feng; Li, Hua; Li, Na-Jun; Chen, Dong-Yun; Lu, Jian-Mei

2017-08-23

Herein, for the first time, quaternary resistive memory based on an organic molecule is achieved via surface engineering. A layer of poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT-PSS) was inserted between the indium tin oxide (ITO) electrode and the organic layer (squaraine, SA-Bu) to form an ITO/PEDOT-PSS/SA-Bu/Al architecture. The modified resistive random-access memory (RRAM) devices achieve quaternary memory switching with the highest yield (∼41%) to date. Surface morphology, crystallinity, and mosaicity of the deposited organic grains are greatly improved after insertion of a PEDOT-PSS interlayer, which provides better contacts at the grain boundaries as well as the electrode/active layer interface. The PEDOT-PSS interlayer also reduces the hole injection barrier from the electrode to the active layer. Thus, the threshold voltage of each switching is greatly reduced, allowing for more quaternary switching in a certain voltage window. Our results provide a simple yet powerful strategy as an alternative to molecular design to achieve organic quaternary resistive memory.

Progress report. Task 1 - quaternary tectonics, 1 October 1991--30 September 1992

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

1992-09-30

Progress is reported on a study concerned with the quaternary tectonics of Yucca Mountain, the proposed site for an underground disposal facility for high-level radioactive wastes. Refinement and revision of crater Flat Quaternary stratigraphy continued and consisted of several activities: revision of rock varnish cation leaching curve; sample comparison of RV manganese;,iron microlaminations;and correlation of Crater Flat allostratigraphic units with regional chronologies.

INTERNATIONAL CONFERENCE ON SEMICONDUCTOR INJECTION LASERS SELCO-87: Simple formula for the thermal conductivity of a quaternary solid solution

NASA Astrophysics Data System (ADS)

Nakwaski, W.

1988-11-01

An analysis is made of the thermal conductivity of quaternary solid solutions (alloys) allowing for their disordered structure on the basis of a phenomenological analysis proposed by Abeles. This method is applied to a quaternary solid solution In1 - xGaxAsyP1 - y. A simple analytic expression is derived for the thermal conductivity of this material.

Advances in the synthesis of α-quaternary α-ethynyl α-amino acids.

PubMed

Boibessot, Thibaut; Bénimélis, David; Meffre, Patrick; Benfodda, Zohra

2016-09-01

α-Quaternary α-ethynyl α-amino acids are an important class of non-proteinogenic amino acids that play an important role in the development of peptides and peptidomimetics as therapeutic agents and in the inhibition of enzyme activities. This review provides an overview of the literature concerning synthesis and applications of α-quaternary α-ethynyl α-amino acids covering the period from 1977 to 2015.

Classification of protein quaternary structure by functional domain composition

PubMed Central

Yu, Xiaojing; Wang, Chuan; Li, Yixue

2006-01-01

Background The number and the arrangement of subunits that form a protein are referred to as quaternary structure. Quaternary structure is an important protein attribute that is closely related to its function. Proteins with quaternary structure are called oligomeric proteins. Oligomeric proteins are involved in various biological processes, such as metabolism, signal transduction, and chromosome replication. Thus, it is highly desirable to develop some computational methods to automatically classify the quaternary structure of proteins from their sequences. Results To explore this problem, we adopted an approach based on the functional domain composition of proteins. Every protein was represented by a vector calculated from the domains in the PFAM database. The nearest neighbor algorithm (NNA) was used for classifying the quaternary structure of proteins from this information. The jackknife cross-validation test was performed on the non-redundant protein dataset in which the sequence identity was less than 25%. The overall success rate obtained is 75.17%. Additionally, to demonstrate the effectiveness of this method, we predicted the proteins in an independent dataset and achieved an overall success rate of 84.11% Conclusion Compared with the amino acid composition method and Blast, the results indicate that the domain composition approach may be a more effective and promising high-throughput method in dealing with this complicated problem in bioinformatics. PMID:16584572

Atomic-scale properties of Ni-based FCC ternary, and quaternary alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tamm, Artur; Aabloo, Alvo; Klintenberg, Mattias

2015-08-26

The aim of our study is to characterize some atomic-scale properties of Ni-based FCC multicomponent alloys. For this purpose, we use Monte Carlo method combined with density functional theory calculations to study short-range order (SRO), atomic displacements, electronic density of states, and magnetic moments in equimolar ternary NiCrCo, and quaternary NiCrCoFe alloys. The salient features for the ternary alloy are a negative SRO parameter between Ni Cr and a positive between Cr Cr pairs as well as a weakly magnetic state. For the quaternary alloy we predict negative SRO parameter for Ni Cr and Ni Fe pairs and positive formore » Cr Cr and Fe Fe pairs. Atomic displacements for both ternary and quaternary alloys are negligible. In contrast to the ternary, the quaternary alloy shows a complex magnetic structure. The electronic structure of the ternary and quaternary alloys shows differences near the Fermi energy between a random solid solution and the predicted structure with SRO. Despite that, the calculated EXAFS spectra does not show enough contrast to discriminate between random and ordered structures. Finally, the predicted SRO has an impact on point-defect energetics, electron phonon coupling and thermodynamic functions and thus, SRO should not be neglected when studying properties of these two alloys.« less

A combined solid-state NMR and X-ray crystallography study of the bromide ion environments in triphenylphosphonium bromides.

PubMed

Burgess, Kevin M N; Korobkov, Ilia; Bryce, David L

2012-04-27

Multinuclear ((31)P and (79/81)Br), multifield (9.4, 11.75, and 21.1 T) solid-state nuclear magnetic resonance experiments are performed for seven phosphonium bromides bearing the triphenylphosphonium cation, a molecular scaffold found in many applications in chemistry. This is undertaken to fully characterise their bromine electric field gradient (EFG) tensors, as well as the chemical shift (CS) tensors of both the halogen and the phosphorus nuclei, providing a rare and novel insight into the local electronic environments surrounding them. New crystal structures, obtained from single-crystal X-ray diffraction, are reported for six compounds to aid in the interpretation of the NMR data. Among them is a new structure of BrPPh(4), because the previously reported one was inconsistent with our magnetic resonance data, thereby demonstrating how NMR data of non-standard nuclei can correct or improve X-ray diffraction data. Our results indicate that, despite sizable quadrupolar interactions, (79/81)Br magnetic resonance spectroscopy is a powerful characterisation tool that allows for the differentiation between chemically similar bromine sites, as shown through the range in the characteristic NMR parameters. (35/37)Cl solid-state NMR data, obtained for an analogous phosphonium chloride sample, provide insight into the relationship between unit cell volume, nuclear quadrupolar coupling constants, and Sternheimer antishielding factors. The experimental findings are complemented by gauge-including projector-augmented wave (GIPAW) DFT calculations, which substantiate our experimentally determined strong dependence of the largest component of the bromine CS tensor, δ(11), on the shortest Br-P distance in the crystal structure, a finding that has possible application in the field of NMR crystallography. This trend is explained in terms of Ramsey's theory on paramagnetic shielding. Overall, this work demonstrates how careful NMR studies of underexploited exotic nuclides, such as (79/81)Br, can afford insights into structure and bonding environments in the solid state. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mapping the North Sea base-Quaternary: using 3D seismic to fill a gap in the geological record

NASA Astrophysics Data System (ADS)

Lamb, Rachel; Huuse, Mads; Stewart, Margaret; Brocklehurst, Simon H.

2014-05-01

The identification and mapping of the base-Quaternary boundary in the central parts of the North Sea is problematic due to the change from an unconformable transition between Pliocene and Pleistocene deltaic deposits in the southern North Sea to a conformable one further north (Sejrup et al 1991; Gatliff et al 1994). The best estimates of the transition use seismic reflection data to identify a 'crenulated reflector' (Buckley 2012), or rely on correlating sparse biostratigraphy (Cameron et al 1987). Recent integration of biostratigraphy, pollen analysis, paleomagnetism and amino acid analysis in the Dutch and Danish sectors (Rasmussen et al 2005; Kuhlmann et al 2006) allows greater confidence in the correlation to a regional 3D seismic dataset and show that the base-Quaternary can be mapped across the entire basin. The base-Quaternary has been mapped using the PGS MegaSurvey dataset from wells in the Danish Sector along the initially unconformable horizon and down the delta front into the more conformable basin giving a high degree of confidence in the horizon pick. The mapped horizon is presented here alongside the difference between this new interpretation and the previously interpreted base-Quaternary (Buckley 2012). The revised base-Quaternary surface reaches a depth of 1248 ms TWT or approximately 1120 m (assuming average velocity of 1800 m/s) showing an elongate basin shape that follows the underlying structure of the Central Graben. The difference between the revised base-Quaternary and the traditional base-Quaternary reaches a maximum of over 600 ms TWT or approximately 540 m in the south-west with over 300 ms TWT or approximately 270 m at the Josephine well (56° 36.11'N, 2° 27.09'E) in the centre of the basin. Mapping this new base-Quaternary allows for the interpretation of the paleo-envionrment during the earliest Quaternary. Seismic attribute analysis indicates a deep water basin with sediment deposition from multiple deltas and redistribution by deep water currents. This has strong implications for both the Quaternary climate archive and petroleum systems in the North Sea. Key Words: base-Quaternary; chronostratigraphy: seismic interpretation; paleoenvironments References Buckley, F.A., (2012) 'An Early Pleistocene grounded ice sheet in the Central North Sea' From: Huuse, M., Redfern, J., Le Heron, D.P., Dixon, R.J., Moscariello, A., Craig, J. (eds) 'Glaciogenic reservoirs and Hydrocarbon Systems' Geological Society, London, Special Publications, 368 Cameron, T.D.J., Stoker, M.S., Long, D., (1987) 'The history of Quaternary sedimentation in the UK sector of the North Sea Basin' Journal of the Geological Society, 144, 43-58 Gatliff, R.W, Richards, P.C, Smith, K, Graham, C.C, McCormac, M, Smith, N.J.P, Long, D, Cameron, T.D.J, Evans, D, Stevenson, A.G, Bulat, J, Ritchie, J.D, (1994) 'United Kingdom offshore regional report: the geology of the central North Sea.' London: HMSO for the British Geological Survey Kulhmann, G., Langereis C.G., Munsterman, D., van Leeuwen, R.-J., Verreussel, R., Meulenkamp, J.E., Wong, Th.E., 2006 'Intergrated chronostratigraphy of the Pliocene-Pliestocene interval and its relation to the regional stratigraphical stages in the Southern North Sea region' Netherlands Journal of Geosciences 85(1), 29-45 Rasmussen, E.A., Vejb?k O.V., Bidstrup, T., Piasecki, S., Dybkj?r, K., 2005 'Late Cenozoic depositional history of the Danish North Sea Basin: implications for the petroleum systems in the Kraka, Halfdan, Siri and Nini fields', Petroleum Geology Conference series 6, 1347-1358 Sejrup, H.P., Aareseth, I., Haflidason, H., 1991 'The Quaternary succession in the northern North Sea' Marine Geology 101 103-111

THE INTERSECTION OF STABLE AND NON-EQUILIBRIUM TETRAHEDRA IN A MUTUAL 7- COMPONENT SYSTEM OF Li, Na, Rb, T1/Br, C1, NO$sub 3$, SO$sub 4$ (in Russian)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dombrovskaya, N.S.; Khakhlova, N.V.; Alekseeva, E.A.

1961-04-21

The most stable configuration of the mixture of the 16 salts formed from Li, Na, Rb, Tl/Br, Cl, NO/sub 3/, and S0/sub 4/ con ture which however interact, resulting in a stable mixture. On the basis of exchange reactions the following equation has been derived: LiBr + NaNO/sub 3/ + RbCl + 1/2Tl/sub 2/SO/sub 4/ = 1/ 2LiSO/sub 4/ + NaCl + RbNO/sub 3/ + TlBr. In addition, several binary complexes are also formed, such as Li/sub 2/SO/sub 4/ - Rb/sub 2/SO/sub 4/, 4Li/sub 2/SO/ sub 4/ - RbSO /sub 4/, RbCl - 2Li/sub 2/SO/sub 4/ and possible others. Inmore » view of the great interest, the intersection of stable and non-equilibrium tetrahedra consisting of components of both, was experimentally studied by thermai analysis. On the basis of cooling curves the following deflection points have been observed: 453 deg C, precipitation of the first Li/sub 2/SO/sub 4/ crystals; 409 deg , coprecipitation of Li/sub 2/SO/sub 4/ and NaCl; 391 deg , coprecipitation of Li/sub 2/SO/sub 4/, NaCl snd TlBr; and finally at 107 deg , formation of the quaternary eutectic with the previously mentioned salts + RbNO/sub 3/. The microstructures of the stable and non-equilibrium phases are quite similar. (TTT)« less

Chemical composition and distribution of lithium-rich brines in salar de Uyuni and nearby salars in southwestern Bolivia

USGS Publications Warehouse

Ericksen, G.E.; Vine, J.D.; Raul, Ballon A.

1978-01-01

Preliminary investigations at Salar de Uyuni and the nearby salars (salt pans) of Coipasa and Empexa in the southern part of the Bolivian Altiplano show the presence of widespread lithium-rich brines. Widely scattered brine samples from Salar de Uyuni, which has an area of about 9000 km2 and is the largest salt pan on earth, show lithium values ranging from 80 to 1500 ppm. High values of 300-700 ppm are most prevalent in an area of about 2500 km2 in the east-central and southeastern part of the salar. A few brine samples in small areas in Coipasa and Empexa Salars have values ranging from 170 to 580 ppm Li. All the brines are essentially saturated with halite and are moderately high in sulfate (5000-15,000 ppm SO4) but low in carbonate (<500 ppm HCO3). Potassium and magnesium values are relatively high, chiefly in the range of 2000-20,000 ppm, and the K Mg ratio is about 1:1. The Li K and Li Mg ratios are relatively constant at about 1:20. The crystalline saline material and brines in these salars are residual from a former large lake, Lago Minchin, that occupied much of the southern Bolivian Altiplano during late Pleistocene time, augmented by saline material carried to the salars by streams since final drying of this lake. Thermal springs associated with rhyolitic volcanic rocks of Quaternary age may have been a major source of the lithium. ?? 1978.

[Research on the marketing status of antimicrobial products and the use of antimicrobial agents indicated on product labels from 1991 through 2005].

PubMed

Nakashima, Harunobu; Miyano, Naoko; Matsunaga, Ichiro; Nakashima, Naomi; Kaniwa, Masa-aki

2007-05-01

To clarify the marketing status of antimicrobial products, descriptions on the labels of commercially available antimicrobial products were investigated from 1991 through 2005, and the results were analyzed using a database system on antimicrobial deodorant agents. A classification table of household antimicrobial products was prepared and revised, based on which target products were reviewed for any changes in the product type. The number of antimicrobial products markedly increased over 3 years starting from 1996, among which there were many products apparently not requiring antimicrobial processing. More recently, in the 2002 and 2004 surveys, while sales of kitchenware and daily necessities decreased, chemical products, baby articles, and articles for pets increased; this poses new problems. To clarify the use of antimicrobial agents in the target products, a 3-step (large, intermediate, small) classification table of antimicrobial agents was also prepared, based on which antimicrobial agents indicated on the product labels were checked. The rate of identifying the agents increased. However, this is because of the increase of chemical products and baby articles, both of which more frequently indicated the ingredient agents on the labels, and the decrease of kitchenware and daily necessities, which less frequently indicated them on the labels. Therefore there has been little change in the actual identification rate. The agents used are characterized by product types: quaternary ammonium salts, metal salts, and organic antimicrobials are commonly used in textiles, plastics, and chemical products, respectively. Since the use of natural organic agents has recently increased, the safety of these agents should be evaluated.

Quaternary dinoflagellate cysts in the Arctic Ocean: Potential and limitations for stratigraphy and paleoenvironmental reconstructions

NASA Astrophysics Data System (ADS)

Matthiessen, Jens; Schreck, Michael; De Schepper, Stijn; Zorzi, Coralie; de Vernal, Anne

2018-07-01

The Arctic Ocean is a siliciclastic depositional environment which lacks any rock-forming biogenic calcareous and siliceous components during large parts of its Quaternary history. These hemipelagic sediments are nevertheless suitable for the study of organic-walled microfossils of which the fossil remains of dinoflagellates - dinoflagellate cysts - are the most important group. Dinoflagellate cysts have become an important tool in paleoceanography of the high northern latitudes, but their potential for Quaternary biostratigraphy has remained largely unexplored. Dinoflagellate cysts are the dominant marine palynomorph group which is more continuously present in the marginal seas (e.g. Barents Sea, Bering Sea) than in the Arctic Ocean itself throughout the Quaternary. Most species have long stratigraphic ranges, are temporary absent and show abundance variations on glacial-interglacial timescales. Of the more than 30 taxa recorded, only Habibacysta tectata and Filisphaera filifera became extinct in the Pleistocene. The highest persistent occurrence of H. tectata at ca. 2.0 Ma and the top of F. filifera acme at ca. 1.8 Ma can be used for supra-regional stratigraphic correlation between the Arctic Ocean and adjacent basins. These events corroborate a slow sedimentation rate model for the Quaternary section on the central Lomonosov Ridge, but a combination of different methods will have to be applied to provide a detailed chronostratigraphy. The occurrence of cysts of phototrophic dinoflagellates in certain stratigraphic intervals on Lomonosov Ridge supports published evidence of episodic opening of the multiyear Arctic sea ice cover during the Quaternary probably related to a stronger inflow of Atlantic water. This contradicts the hypothesis of a permanently ice covered central Arctic Ocean in the Quaternary.

A novel assay to measure tertiary and quaternary amines in wastewater: An indicator for NDMA wastewater precursors.

PubMed

Woods-Chabane, Gwen C; Glover, Caitlin M; Marti, Erica J; Dickenson, Eric R V

2017-07-01

This study examined the potential of using a novel bulk amine assay as an approximation for the tertiary and quaternary amine load in wastewaters and surface water samples, and this approximation was compared to N-nitrosodimethylamine (NDMA) formation potential using chloramines. An existing colorimetric method was examined and optimized for the detection of amines in environmental water samples. The method consists of liquid-liquid extraction followed by a catalyzed reaction to form a yet-undefined product that is known to be both a strong chromophore and fluorophore. Previous work verified that this reaction was effectively catalyzed by a number of compounds containing tertiary and quaternary amine moieties. Many tertiary and quaternary compounds are also efficient producers of NDMA under chloramination conditions, and a linear correlation was consequently derived from the bulk amine signals vs. NDMA formation potential in various wastewater samples (R 2  = 0.74; n = 24; p-value < 0.05). The results provide evidence that approximately 2% of the tertiary and quaternary amines measured can form NDMA and an estimated 0.01-1.3% of nitrogen in dissolved organic nitrogen originates from these bulk amines. The normalization of NDMA concentration by the amine measurement revealed that ozone effectively destroyed those tertiary and quaternary amine structures more likely to form NDMA in treated wastewater samples. This bulk amine assay illustrates that proxy measurements of tertiary and quaternary amines can be linked to the NDMA formation potential of a given sample, and this approach may prove useful as a characterizing tool for NDMA precursors in wastewater. Copyright © 2017 Elsevier Ltd. All rights reserved.

Quaternary vertebrate faunas from Sumba, Indonesia: implications for Wallacean biogeography and evolution

PubMed Central

Crees, Jennifer J.; Hansford, James; Jeffree, Timothy E.; Crumpton, Nick; Kurniawan, Iwan; Setiyabudi, Erick; Paranggarimu, Umbu; Dosseto, Anthony; van den Bergh, Gerrit D.

2017-01-01

Historical patterns of diversity, biogeography and faunal turnover remain poorly understood for Wallacea, the biologically and geologically complex island region between the Asian and Australian continental shelves. A distinctive Quaternary vertebrate fauna containing the small-bodied hominin Homo floresiensis, pygmy Stegodon proboscideans, varanids and giant murids has been described from Flores, but Quaternary faunas are poorly known from most other Lesser Sunda Islands. We report the discovery of extensive new fossil vertebrate collections from Pleistocene and Holocene deposits on Sumba, a large Wallacean island situated less than 50 km south of Flores. A fossil assemblage recovered from a Pleistocene deposit at Lewapaku in the interior highlands of Sumba, which may be close to 1 million years old, contains a series of skeletal elements of a very small Stegodon referable to S. sumbaensis, a tooth attributable to Varanus komodoensis, and fragmentary remains of unidentified giant murids. Holocene cave deposits at Mahaniwa dated to approximately 2000–3500 BP yielded extensive material of two new genera of endemic large-bodied murids, as well as fossils of an extinct frugivorous varanid. This new baseline for reconstructing Wallacean faunal histories reveals that Sumba's Quaternary vertebrate fauna, although phylogenetically distinctive, was comparable in diversity and composition to the Quaternary fauna of Flores, suggesting that similar assemblages may have characterized Quaternary terrestrial ecosystems on many or all of the larger Lesser Sunda Islands. PMID:28855367

Variation in Inflammatory/Regulatory Cytokines in Secondary, Tertiary, and Quaternary Challenges with Dengue Virus

PubMed Central

Sierra, Beatriz; Pérez, Ana B.; Alvarez, Mayling; García, Gissel; Vogt, Katrin; Aguirre, Eglys; Schmolke, Kathrin; Volk, Hans-Dieter; Guzmán, María G.

2012-01-01

Secondary heterologous dengue infection is a risk factor for severe disease manifestations because of the immune-enhancement phenomenon. Succeeding clinical infections are seldom reported, and the clinical course of tertiary and quaternary dengue infections is not clear. Cuba represents a unique environment to study tertiary/quaternary dengue infections in a population with known clinical and serologic dengue markers and no dengue endemicity. We took advantage of this exceptional epidemiologic condition to study the effect of primary, secondary, tertiary, and quaternary dengue infection exposure on the expression of pro-inflammatory and regulatory cytokines, critical in dengue infection pathogenesis, by using a dengue infection ex vivo model. Whereas secondary exposure induced a high cytokine response, we found a significantly lower expression of tumor necrosis factor-α, interferon-γ, interleukin-10, and tumor growth factor-β after tertiary and quaternary infectious challenge. Significant differences in expression of the cytokines were seen between the dengue immune profiles, suggesting that the sequence in which the immune system encounters serotypes may be important in determining the nature of the immune response to subsequent infections. PMID:22802438

A study of Quaternary structures in the Qom region, West Central Iran

NASA Astrophysics Data System (ADS)

Babaahmadi, A.; Safaei, H.; Yassaghi, A.; Vafa, H.; Naeimi, A.; Madanipour, S.; Ahmadi, M.

2010-12-01

West Central Iran comprises numerous Quaternary faults. Having either strike-slip or thrust mechanisms, these faults are potentially active and therefore capable of creating destructive earthquakes. In this paper, we use satellite images as well as field trips to identify these active faults in the Qom region. The Qom and Indes faults are the main NW-trending faults along which a Quaternary restraining step-over zone has formed. Kamarkuh, Mohsen Abad, and Ferdows anticlines are potentially active structures that formed in this restraining step-over zone. There are some thrusts and anticlines, such as the Alborz anticline and Alborz fault, which are parallel to strike-slip faults such as the Qom fault, indicating deformation partitioning in the area. In addition to NW-trending structures, there is an important NE-trending fault known as the Qomrud fault that has deformed Quaternary deposits and affected Kushk-e-Nosrat fault, Alborz anticline, and Qomrud River. The results of this study imply that the major Quaternary faults of West Central Iran and their restraining step-over zones are potentially active.

Ancient dna from pleistocene fossils: Preservation, recovery, and utility of ancient genetic information for quaternary research

NASA Astrophysics Data System (ADS)

Yang, Hong

Until recently, recovery and analysis of genetic information encoded in ancient DNA sequences from Pleistocene fossils were impossible. Recent advances in molecular biology offered technical tools to obtain ancient DNA sequences from well-preserved Quaternary fossils and opened the possibilities to directly study genetic changes in fossil species to address various biological and paleontological questions. Ancient DNA studies involving Pleistocene fossil material and ancient DNA degradation and preservation in Quaternary deposits are reviewed. The molecular technology applied to isolate, amplify, and sequence ancient DNA is also presented. Authentication of ancient DNA sequences and technical problems associated with modern and ancient DNA contamination are discussed. As illustrated in recent studies on ancient DNA from proboscideans, it is apparent that fossil DNA sequence data can shed light on many aspects of Quaternary research such as systematics and phylogeny. conservation biology, evolutionary theory, molecular taphonomy, and forensic sciences. Improvement of molecular techniques and a better understanding of DNA degradation during fossilization are likely to build on current strengths and to overcome existing problems, making fossil DNA data a unique source of information for Quaternary scientists.

Palladium-Catalyzed Asymmetric Alkylation in the Synthesis of Cyclopentanoid and Cycloheptanoid Core Structures Bearing All-Carbon Quaternary Stereocenters

PubMed Central

Hong, Allen Y.; Bennett, Nathan B.; Krout, Michael R.; Jensen, Thomas; Harned, Andrew. M.

2011-01-01

General catalytic asymmetric routes toward cyclopentanoid and cycloheptanoid core structures embedded in numerous natural products have been developed. The central stereoselective transformation in our divergent strategies is the enantioselective decarboxylative alkylation of seven-membered β-ketoesters to form α-quaternary vinylogous esters. Recognition of the unusual reactivity of β-hydroxyketones resulting from the addition of hydride or organometallic reagents enabled divergent access to γ-quaternary acylcyclopentenes through a ring contraction pathway or γ-quaternary cycloheptenones through a carbonyl transposition pathway. Synthetic applications of these compounds were explored through the preparation of mono-, bi-, and tricyclic derivatives that can serve as valuable intermediates for the total synthesis of complex natural products. This work complements our previous work with cyclohexanoid systems. PMID:22347731

Quaternary Tectonic and Climatic Processes shaping the Central Andean hyperarid forearc (southern Peru)

NASA Astrophysics Data System (ADS)

Audin, Laurence; Benavente, Carlos; Zerathe, Swann; Saillard, Marianne; Hall, Sarah R.; Farber, Daniel L.

2015-04-01

Understanding the forearc structure and processes related to Quaternary evolution and uplift of the Western Andean Cordillera remains an outstanding scientific issue. Models of Andean Plateau evolution based on Tertiary volcanic stratigraphy since 5Ma suggest that the deformation was focused along the eastern margin of the plateau and that minimal uplift occurred along the Pacific margin. On the contrary, new tectonic data and Quaternary surface 10Be dating highlight the presence of recently active deformation, incision and alluvial processes within the upper Andean forearc together with a regional uplift of the coastal zone. Additionally, the high obliquity observed in the northern Arica Bend region makes it an ideal target to discuss whether partitioning of the oblique convergence is accommodated by the neotectonic features that dissect the Quaternary forearc. Our goals are both to decipher the Quaternary tectonic and climatic processes shaping the hyperarid forearc along strike and across strike. Finally, we aim to quantify the respective influence of these factors in the overall uplift of the Western Andes. Indeed, sequences of pediment surfaces, landslide products, paleolake deposits and marine terraces found along the oblique Peruvian margin are a unique set of datable markers that can be used to quantify the rates of Quaternary processes. In this study, we focus on the southern Peru hyperarid Atacama area where regional surfaces and tectonic markers (scarps, folds, temporary streams and paleolake levels offsets…) are well preserved for the Quaternary timescale. Numerous landsliding events align on the major fault segments and reflect Plio-Pleistocene climatic and tectonic activity together with filled and strath terraces. As the present day sea-level is one of the highest levels recorded for Quaternary time span, any emerged marine terrace is preserved by tectonic coastal uplift. In particular, the geomorphic and chronologic correlation between marine and continental planation surfaces or terraces permit to deduce net vertical rates and suggests that the along strike uplift affected not only the coast but also the overall ~50 km-wide forearc of the Western Andes. We produced a chronology of remnant low-relief surfaces and a new neotectonic map of the Central Andean forearc between ~14° and 18°S based on detailed field mapping and 10Be cosmogenic dating. We address 1) the spatial and temporal correlations of various markers, and 2) the correlation of the surface abandonment ages to various regional climatic events and 3) the description of neotectonic activity accommodating both uplift and partitioning. Multiple markers yield 10Be surface abandonment ages that spanning 35 ka to >2 Ma. Erosion surfaces >2 Ma yield low erosion rates of <0.1mm/yr. However uplift rates of ~0.1-1mm/yr and multiple surfaces dated at ~35 ka suggest that the hyperarid forearc landscape has been recently modified through Quaternary surface uplift and climatic events, contradicting the Miocene fossil forearc hypothesis. Generally, surface abandonment ages and activated landslides periods tend to correlate with cold wet periods preceding Plio Pleistocene deglaciation on the Altiplano. Finally, neotectonic oblique faults connecting at depth participate to topography building in the Arica Bend region and suggest that Quaternary surface abandonment is the result of both surface uplift in the forearc and specific high-discharge climate periods in the high Andes. Obtained Quaternary regional uplift rates and individual slip-rates suggest that the Andean forearc may accommodate as much as 0.5 to 1 mm/yr of regional uplift for the Quaternary time period.

Reversed-phase high-performance liquid chromatography of unsubstituted aminobenzoic acids

USGS Publications Warehouse

Abidi, S.L.

1989-01-01

High-performance liquid chromatographic (HPLC) characteristics of three position isomers of aminobenzoic acids (potential metabolites of important anesthetic drugs), were delineated with respect to their interactions with various mobile phases and stationary phases. HPLC with five hydrocarbonaceous phase, I?-cyclodextrin silica (CDS), macrophase MP-1 polymer (MP), macroporous polystyrene/divinylbenzene (MPD), octadecylsilica (ODS), and propylphenylsilica (PPS), yielded results explicable in terms of substituent effects derived from the bifunctional amino- and carboxy groups. For cases where mobile phases contained sulfonates or quaternary ammonium salts both having longer chain alkyls, retention of analytes on all but CDS appeared to proceed predominantly via an ion-pairing mechanism. The extent of the corresponding counter-ion effects decreased in the order: MPD > ODS > PPS > MP, while the analyte retention order paralleled thier pH2 values. On the other hand, an inverse relationship between the magnitude of capacity factors (k') and pK1 values of the title compounds was observed in experiments that produced retention data incompatible with ion-pair interaction rationales. The unique HPLC results obtained with the CDS phase are compared with those obtained with other phases.

Preparing nuclei from cells in monolayer cultures suitable for counting and for following synchronized cells through the cell cycle.

PubMed

Butler, W B

1984-08-15

A procedure is described for preparing nuclei from cells in monolayer culture so that they may be counted using an electronic particle counter. It takes only 10 to 15 min, and consists of swelling the cells in hypotonic buffer and then lysing them with the quaternary ammonium salt, ethylhexadecyldimethylammonium bromide. The cells are completely lysed, yielding a suspension of clean single nuclei which is stable, free of debris, and easily counted. The method was developed for a cell line of epithelial origin (MCF-7), which is often difficult to trypsinize to single cells. It works equally well at all cell densities up to and beyond confluence, and has been used with a variety of cells in culture, including 3T3 cells, bovine macrophages, rat mammary epithelial cells, mouse mammary tumor cell lines, and human fibroblasts. The size of the nuclei produced by this procedure is related to their DNA content, and the method is thus suitable for following cultures of synchronized cells through the cell cycle, and for performing differential counts of cells with substantial differences in DNA content.

Novel Gemini cationic surfactants as anti-corrosion for X-65 steel dissolution in oilfield produced water under sweet conditions: Combined experimental and computational investigations

NASA Astrophysics Data System (ADS)

Migahed, M. A.; elgendy, Amr.; EL-Rabiei, M. M.; Nady, H.; Zaki, E. G.

2018-05-01

Two new sequences of Gemini di-quaternary ammonium salts were synthesized characterized by FTIR and 1HNMR spectroscopic techniques and evaluated as corrosion inhibitor for X-65 steel dissolution in deep oil wells formation water saturated with CO2. The anti-corrosion performance of these compounds was studied by different electrochemical techniques i.e. (potentiodynamic polarization and AC impedance methods), Surface morphology (SEM and EDX) analysis and quantum chemical calculations. Results showed that the synthesized compounds were of mixed-type inhibitors and the inhibition capability was influenced by the inhibitor dose and the spacer substitution in their structure as indicated by Tafel plots. Surface active parameters were determined from the surface tension profile. The synthesized compounds adsorbed via Langmuir adsorption model with physiochemical adsorption as inferred from the standard free energy (ΔG°ads) values. Surface morphology (SEM and EDX) data for inhibitor (II) shows the development of adsorbed film on steel specimen. Finally, the experimental results were supported by the quantum chemical calculations using DFT theory.

Enhanced removal of lead from contaminated soil by polyol-based deep eutectic solvents and saponin

NASA Astrophysics Data System (ADS)

Mukhopadhyay, Soumyadeep; Mukherjee, Sumona; Hayyan, Adeeb; Hayyan, Maan; Hashim, Mohd Ali; Sen Gupta, Bhaskar

2016-11-01

Deep eutectic solvents (DESs) are a class of green solvents analogous to ionic liquids, but less costly and easier to prepare. The objective of this study is to remove lead (Pb) from a contaminated soil by using polyol based DESs mixed with a natural surfactant saponin for the first time. The DESs used in this study were prepared by mixing a quaternary ammonium salt choline chloride with polyols e.g. glycerol and ethylene glycol. A natural surfactant saponin obtained from soapnut fruit pericarp, was mixed with DESs to boost their efficiency. The DESs on their own did not perform satisfactory due to higher pH; however, they improved the performance of soapnut by up to 100%. Pb removal from contaminated soil using mixture of 40% DES-Gly and 1% saponin and mixture of 10% DES-Gly and 2% saponin were above 72% XRD and SEM studies did not detect any major corrosion in the soil texture. The environmental friendliness of both DESs and saponin and their affordable costs merit thorough investigation of their potential as soil washing agents.

Biokinetic Analysis and Metabolic Fate of 2,4-D in 2,4-D-Resistant Soybean (Glycine max).

PubMed

Skelton, Joshua J; Simpson, David M; Peterson, Mark A; Riechers, Dean E

2017-07-26

The Enlist weed control system allows the use of 2,4-D in soybean but slight necrosis in treated leaves may be observed in the field. The objectives of this research were to measure and compare uptake, translocation, and metabolism of 2,4-D in Enlist (E, resistant) and non-AAD-12 transformed (NT, sensitive) soybeans. The adjuvant from the Enlist Duo herbicide formulation (ADJ) increased 2,4-D uptake (36%) and displayed the fastest rate of uptake (U 50 = 0.2 h) among treatments. E soybean demonstrated a faster rate of 2,4-D metabolism (M 50 = 0.2 h) compared to NT soybean, but glyphosate did not affect 2,4-D metabolism. Metabolites of 2,4-D in E soybean were qualitatively different than NT. Applying 2,4-D-ethylhexyl ester instead of 2,4-D choline (a quaternary ammonium salt) eliminated visual injury to E soybean, likely due to the time required for initial de-esterification and bioactivation. Excessive 2,4-D acid concentrations in E soybean resulting from ADJ-increased uptake may significantly contribute to foliar injury.

Synthesis, characterization and antibacterial properties of dihydroxy quaternary ammonium salts with long chain alkyl bromides.

PubMed

Liu, Wen-Shuai; Wang, Chun-Hua; Sun, Ju-Feng; Hou, Gui-Ge; Wang, Yu-Peng; Qu, Rong-Jun

2015-01-01

Five N-methyl-N-R-N,N-bis(2-hydroxyethyl) ammonium bromides (R = -benzyl (chloride, BNQAS), -dodecyl (C12QAS), -tetradecyl (C14QAS), -hexadecyl (C16QAS), -octadecyl (C18QAS)) were prepared based on N-methyldiethanolamine (MDEA) and halohydrocarbon. Five QAS were characterized by FTIR, NMR, and MS. BNQAS, C12QAS, C14QAS, and C16QAS were confirmed by X-ray single-crystal diffraction. Their antibacterial properties indicated good antibacterial abilities against E. coli, S. aureus, B. subtilis, especially C12QAS with the best antibacterial ability (100% to E. coli, 95.65% to S. aureus, and 91.41% to B. subtilis). In addition, C12QAS also displayed the best antifungal activities than BNQAS and C18QAS against Cytospora mandshurica, Botryosphaeria ribis, Physalospora piricola, and Glomerella cingulata with the ratio of full marks. The strategy provides a facile way to design and develop new types of antibacterial drugs for application in preventing the fruit rot, especially apple. © 2014 John Wiley & Sons A/S.

Rapid, Microwave-Assisted Synthesis of Cubic, Three-Dimensional, Highly Porous MOF-205 for Room Temperature CO2 Fixation via Cyclic Carbonate Synthesis.

PubMed

Babu, Robin; Roshan, Roshith; Kathalikkattil, Amal Cherian; Kim, Dong Woo; Park, Dae-Won

2016-12-14

A dual-porous, three-dimensional, metal-organic framework [Zn 4 O(2,6-NDC)(BTB) 4/3 ] (MOF-205, BET = 4200 m 2 /g) has been synthesized using microwave power as an alternative energy source for the first time, and its catalytic activity has been exploited for CO 2 -epoxide coupling reactions to produce five-membered cyclic carbonates under solvent-free conditions. Microwave synthesis was performed at different time intervals to reveal the formation of the crystals. Significant conversion of various epoxides was obtained at room temperature, with excellent selectivity toward the desired five-membered cyclic carbonates. The importance of the dual porosity and the synergistic effect of quaternary ammonium salts on efficiently catalyzed CO 2 conversion were investigated using various experimental and physicochemical characterization techniques, and the results were compared with those of the solvothermally synthesized MOF-205 sample. On the basis of literature and experimental inferences, a rationalized mechanism mediated by the zinc center of MOF-205 for the CO 2 -epoxide cycloaddition reaction has been proposed.

Removal of the commercial pesticides Novadim Progress, Bordeaux mixture and Karate Zeon by pullulan derivatives based flocculants.

PubMed

Ghimici, Luminita; Constantin, Marieta

2018-04-14

Cationic pullulan derivatives have been synthesized and evaluated, for the first time, as flocculants for the separation of the commercial pesticides, Novadim Progress (organophosphoric type), Bordeax mixture and Karate Zeon (pyrethroid type) from synthetic wastewater. The investigated polymer samples contained either pendent tertiary amine or quaternary ammonium salts groups. The separation efficiency was followed by UV-Vis spectroscopy, while the information regarding the mechanism involved in the separation of pesticide particles have been obtained by zeta potential. UV-Vis spectroscopy data showed strong pesticide particles/polycation interactions in case of Novadim Progress and Bordeaux mixture (maximum pesticide removal between 90% and 98%). Good separation efficiency (around 80%) of Karate Zeon emulsion was also noticed. The zeta potential measurements indicated that the charge neutralization was the common flocculation mechanism for the removal of these pesticides. In addition, the hydrogen bondings and chelation of copper ions by amide and/or tertiary amino groups of the polycations had a noteworthy contribution to the pesticide removal. Copyright © 2018 Elsevier Ltd. All rights reserved.

A major change in precipitation gradient on the Chinese Loess Plateau at the Pliocene-Quaternary boundary

NASA Astrophysics Data System (ADS)

Peng, Wenbin; Nie, Junsheng; Wang, Zhao; Qiang, Xiaoke; Garzanti, Eduardo; Pfaff, Katharina; Song, Yougui; Stevens, Thomas

2018-04-01

Spatiotemporal variations in East Asian Monsoon (EAM) precipitation during the Quaternary have been intensively studied. However, spatial variations in pre-Quaternary EAM precipitation remain largely uninvestigated, preventing a clear understanding of monsoon dynamics during a warmer climatic period. Here we compare the spatial differences in heavy mineral assemblages between Quaternary loess and pre-Quaternary Red Clay on the Chinese Loess Plateau (CLP) to analyze spatial patterns in weathering. Prior studies have revealed that unstable hornblende is the dominant (∼50%) heavy mineral in Chinese loess deposited over the past 500 ka, whereas hornblende content decreases to <10% in strata older than ∼1 Ma in the central CLP because of diagenesis. In the present study we found that hornblende is the dominant heavy mineral in 2-2.7 Ma loess on the northeastern CLP (at Jiaxian), which today receives little precipitation. Conversely, hornblende content in the upper Miocene-Pliocene Red Clay at Jiaxian is <10%, as in the central CLP. The early Quaternary abundance of hornblende at Jiaxian indicates that the current northwestward-decreasing precipitation pattern and consequent dry climate at Jiaxian must have been initiated since ∼2.7 Ma, preventing hornblende dissolution to amounts <10% as observed in the central CLP. By contrast, the 7 Ma and 3 Ma Jiaxian Red Clay hornblende content is significantly less than that of the Xifeng samples, despite the fact that today Xifeng receives more precipitation than Jiaxian, with expected enhanced hornblende weathering. This suggests that the northeastern CLP received more precipitation during the Late Miocene-Pliocene than at Xifeng, indicating that the precipitation gradient on the CLP was more east-west during the Late Miocene-Pliocene rather than northwest-southeast as it was in the Quaternary. A comparison of magnetic susceptibility records for these sections confirms this inference. We attribute this major change in climatic patterns at ∼2.7 Ma to decreased northward moisture transportation associated with Northern Hemisphere glaciation and cooling in the Quaternary. This study therefore demonstrates the potential usefulness of employing heavy mineral analysis in both paleoclimatic and paleooceanographic reconstructions.

Prevalence of IgE against neuromuscular blocking agents in hairdressers and bakers.

PubMed

Dong, S; Acouetey, D S; Guéant-Rodriguez, R-M; Zmirou-Navier, D; Rémen, T; Blanca, M; Mertes, P M; Guéant, J-L

2013-11-01

Allergic IgE-mediated reactions to neuromuscular blocking agents (NMBAs) are the main cause of immediate hypersensitivity reactions in anaesthesia; their predominant occurrence in the absence of previous exposure to NMBAs suggests a risk related to environmental exposure. To investigate the prevalence of specific IgE to quaternary ammonium ions in two populations professionally exposed to quaternary ammonium compounds, in the north-eastern France. The study had a retrospective follow-up design whereby apprentices were assessed after their 2-year training period as apprentices. The professionally exposed hairdresser populations (n = 128) were compared with baker/pastry makers (n = 108) and 'non-exposed' matched control subjects (n = 379). We observed a 4.6-fold higher frequency of positive IgE against quaternary ammonium ions in hairdressers (HD), compared with baker/pastry makers (BP) and control (C) groups. The competitive inhibition of quaternary ammonium Sepharose radioimmunoassay (QAS-IgE RIA) with succinylcholine was significantly higher in HD, compared with BP and C groups, with inhibition percentage of 66.2 ± 7.4, 39.7 ± 6.0 and 43.8 ± 9.9, respectively (P < 0.001). The specific IgE against quaternary ammonium ions recognized also two compounds widely used by hairdressers, benzalkonium chloride and polyquaternium-10, in competitive inhibition of IgE RIA. When considering the whole study population, hairdresser professional exposure and total IgE > 100 kU/L were the two significant predictors of IgE-sensitization against quaternary ammonium ions in the multivariate analysis of a model that included age, sex, professional exposure, increased concentration of total IgE (IgE > 100 kU/L) and positive IgE against prevalent allergens (Phadiatop(®) ; P = 0.019 and P = 0.001, respectively). The exposure to hairdressing professional occupational factors increases IgE-sensitization to NMBAs and quaternary ammonium ion compounds used in hairdressing. Besides the pholcodine hypothesis, our study suggests that repetitive exposure to quaternary ammonium compounds used in hairdressing is a risk factor for NMBAs sensitization. © 2013 John Wiley & Sons Ltd.

Compression behavior of quaternary and higher order solid-solution L1(2) trialuminides

NASA Technical Reports Server (NTRS)

Kumar, K. S.; Brown, S. A.

1992-01-01

Results from preliminary studies undertaken to evaluate the existence of single-phase L1(2) solid solutions between pairs of ternary L1(2) trialuminides are presented. Two-kilogram ingots of selected quaternary compositions were cast, homogenized and forged into pancakes; compression specimens were machined from the forgings and tested as a function of temperature. The results are compared against existing data for the ternary alloys. The ternary L1(2) trialuminides Al66Ti25Mn9, Al67Ti25Cr8, and Al22Ti8Fe3 were found to exhibit continuous solubility in one another. The quaternary Cr-Mn composition does not indicate any strength advantage over its ternary counterparts. The continuous replacement of Mn with Fe enhances the strength of the quaternary compound over the ternary Al66Ti25 Mn9.

Sex allocation and functional bias of quaternary and quinary flowers on same inflorescence in the hermaphrodite Ruta graveolens

NASA Astrophysics Data System (ADS)

Tang, Jing-Yu; Ren, Ming-Xun

2011-09-01

Intra-inflorescence variation in floral traits is important to understand the pollination function of an inflorescence and the real reproductive outputs of a plant. Ruta graveolens (Rutaceae) produce both quaternary (four petals and eight stamens) and quinary (five petals and ten stamens) flowers on the same cymes, while their pollination roles and the effects on the reproductive success remained unexplored. We experimentally examined the biomass of female versus male organs and pollen viability and stigma receptivity to explore the sex allocation patterns between the flowers. The breeding systems and reproductive outputs through either female function (seed set) or male function (pollen dispersal) were also studied for quinary and quaternary flowers to determine whether there was functional bias. The results showed that R. graveolens was protandrous, with a mixed mating system. Its stamens could slowly move one by one and only dehisce when positioning at the flower center, which could greatly enhance pollen dispersal. The first-opened quinary flower allocated significantly higher resources (dry biomass) in female organs while quaternary flowers allocated more resource in male organs. The quaternary flowers experienced higher pollen limitation in seed production but were more successful in pollen dispersal and the quinary flowers reproduced both through female and male functions. Our data suggested that quinary and quaternary flower on same inflorescence in R. graveolens functioned mainly as the sex role that most resources were allocated, which probably reflect an adaptation for floral phenology and pollination process in this plant.

Environmental Impact Assessment of Dumpsite: Case Study from southwestern Saudi Arabia

NASA Astrophysics Data System (ADS)

Alfaifi, H. J.; Alhumidan, S. M.; Kahal, A. Y.; Abdel Rahman, K.; Al-Qadasi, B.

2017-12-01

The dumpsite is underlain by highly fractured Precambrian basement complex of metamorphosed igneous and sedimentary rocks. Minor Tertiary, Quaternary basalts and Quaternary alluvial deposits overlie the basement rocks. Structurally, the area is affected by intersected series of north-to northwest trending faults. Hydrogeological setting of the study area is characterized by shallow groundwater aquifers in the fractured and weathered basement rocks. Moreover, the area exposes heavy rains especially during summer seasons, which may accelerate the transferring of contaminated water to the neighbouring valleys and low land. At present, the residential and Khamis Mushait new industrial zone are situated close to the dumpsite. The main objective of this study is to assess the leachate intrusion and groundwater contamination in the urban area of Khamis Mushait. Geophysical and geochemical techniques have been successfully applied in the assessment of environmental impact of dumpsites globally. Near-surface geophysical investigations such as Seismic refraction tomography, Schlumberger vertical electrical soundings (VES) and ground magnetic survey have been conducted to detect the controlling structures and lithological variation of the dumpsite. In addition, four water samples from hand dug wells and two surface water samples were collected from and around dumpsite. These water samples were analysed geochemically to inspect the presence of heavy metals, salts (sulphates, nitrates and chlorides), radioactive elements and physically to assess pH, TDS, DO, salinity, total hardness, turbidity, electrical conductivity and temperature. Results of VES illustrate low resistivity zones (≤ 30 Ohm-m) due to conductive leachate from dumpsite while seismic models and ground magnetic intensity map delineated fractures beneath the weathered basement layer which may provide pathways for the contaminants. The physico-chemical analysis of the collected groundwater samples revealed that there are considerable impacts of dumpsite leachate in the shallow groundwater. pH values of the representative samples indicate its unsuitability for human consumption. Leachate flow direction is oriented NNW-SSE and follows the similar flow pattern as deduced from hydrogeological investigation.

Effects of ammonium-based ionic liquids and 2,4-dichlorophenol on the phospholipid fatty acid composition of zebrafish embryos.

PubMed

Piotrowska, Aleksandra; Syguda, Anna; Wyrwas, Bogdan; Chrzanowski, Lukasz; Luckenbach, Till; Heipieper, Hermann J

2018-01-01

Ionic liquids consisting of a combination of herbicidal anions with a quaternary ammonium cation act as efficient herbicides, which are under consideration to be used in the agriculture. In the present study, we used embryos of the zebrafish (Danio rerio) as a model to assess the toxic potential of ammonium-based ionic liquids for aquatic organisms. As we assumed interference of the partially hydrophobic ionic liquid cation with lipids, we investigated the adaptation response in the lipid composition of the zebrafish embryos, triggered by the ionic compound. Therefore, the impact of ammonium-based ionic liquids with different lengths of the alkyl chain ([C6,C6,C1,C1N][Br], [C8,C8,C1,C1N][Br]) on the phospholipid fatty acid (PLFA) profile of zebrafish embryos up to 72 hours post fertilization (hpf) was examined. Furthermore, the changes in the unsaturation index (UI) of PLFAs, as the sum parameter of membrane fluidity in eukaryotic cells, were presented. The PLFA's UI in the zebrafish embryos upon exposure to quaternary ammonium salts was compared to the UI of the embryos upon exposure to nonionic 2,4-dichlorophenol, which has a similar hydrophobicity but is structurally different to [C8,C8,C1,C1N][Br]. It was shown that for ammonium-based ionic liquid precursors non-specific mode of action occurs and the toxic effect on lipid composition of zebrafish embryos can be well predicted based on chemical properties, like hydrophobicity. Furthermore, the changes in PLFAs, expressed by the UI, can be useful to study toxic effects of organic contamination. However, for zebrafish embryos, after ionic liquids and 2,4-DCP exposure, the changes were observed at high lethal concentrations, which caused the incidence of lethality of 30 and 50% of a group of test animals.

Wetlands and Paleolakes in the Hyperarid Atacama Desert During the Late Quaternary and Their Implications for Early Human Occupation of South America

NASA Astrophysics Data System (ADS)

Pfeiffer, M.; Latorre Hidalgo, C.; Santoro, C.; Gayo, E.; McRostie, V.; Finstad, K. M.; Amundson, R.

2016-12-01

The hyperarid Atacama Desert has long been considered a natural barrier to human dispersal. However, several archaeological sites dating from the late Pleistocene have been recently reported on, and other as yet unpublished evidence is rapidly accumulating. It has been established that these occupations were facilitated by increased fluvial activity and biologically productive riparian ecosystems along the western slope of the Andes, and that the presence of humans disappeared with declines in this water flow. The considerable evidence for regional stream flow suggests that basins and lowlands should have contained lakes or wetlands contemporaneous with the ages of the fluvial activity, but there has been no published data on late Quaternary lakes in the region. Here, we report on our observations that possibly many present day salars (salt covered basins) were fresh water lakes and marshlands during the Central Andean Pluvial Event (CAPE) that occurred during the late Pleistocene and early Holocene. We performed radiocarbon analysis of described stratigraphic profiles on paleo-shorelines or in paleo-lake basins that lie within the Pampa del Tamarugal (PDT) basin. We additionally described gastropods, plant remnants, phytoliths and diatomea, which provide a reliable source for paleoenvironmental facies interpretation. These data indicate that a paleolake existed at the location of the present-day Salar de Bellavista, and that wetlands (and possibly lakes) were present at the Salar de Llamara and Pintados. These past aquatic systems are coeval with the activation of the riparian systems of the PDT reported by previous studies. Furthermore, they would have contributed to a starkly different set of resource constraints for early inhabitants than the inhospitable conditions existing today. Additionally, the presence of these water sources provides guidance in the search for additional evidence of human occupation in the region, and for understanding the geographical connections that existed among these earliest inhabitants of the Western Hemisphere.

Ion-pair partition of quarternary ammonium drugs: the influence of counter ions of different lipophilicity, size, and flexibility.

PubMed

Takács-Novák, K; Szász, G

1999-10-01

The ion-pair partition of quaternary ammonium (QA) pharmacons with organic counter ions of different lipophilicity, size, shape and flexibility was studied to elucidate relationships between ion-pair formation and chemical structure. The apparent partition coefficient (P') of 4 QAs was measured in octanol/pH 7.4 phosphate buffer system by the shake-flask method as a function of molar excess of ten counter ions (Y), namely: mesylate (MES), acetate (AC), pyruvate (PYRU), nicotinate (NIC), hydrogenfumarate (HFUM), hydrogenmaleate (HMAL), p-toluenesulfonate (PTS), caproate (CPR), deoxycholate (DOC) and prostaglandin E1 anion (PGE1). Based on 118 of highly precise logP' values (SD< 0.05), the intrinsic lipophilicity (without external counter ions) and the ion-pair partition of QAs (with different counter ions) were characterized. Linear correlation was found between the logP' of ion-pairs and the size of the counter ions described by the solvent accessible surface area (SASA). The lipophilicity increasing effect of the counter ions were quantified and the following order was established: DOC approximate to PGE1 > CPR approximate to PTS > NIC approximate to HMAL > PYRU approximate to AC approximate to MES approximate to HFUM. Analyzing the lipophilicity/molar ratio (QA:Y) profile, the differences in the ion-pair formation were shown and attributed to the differences in the flexibility/rigidity and size both of QA and Y. Since the largest (in average, 300 X) lipophilicity enhancement was found by the influence of DOC and PGE1 and considerable (on average 40 X) increase was observed by CPR and PTS, it was concluded that bile acids and prostaglandin anions may play a significant role in the ion-pair transport of quaternary ammonium drugs and caproic acid and p-toluenesulfonic acid may be useful salt forming agents to improve the pharmacokinetics of hydrophilic drugs.

Effects of ammonium-based ionic liquids and 2,4-dichlorophenol on the phospholipid fatty acid composition of zebrafish embryos

PubMed Central

Piotrowska, Aleksandra; Syguda, Anna; Wyrwas, Bogdan; Chrzanowski, Lukasz; Luckenbach, Till

2018-01-01

Ionic liquids consisting of a combination of herbicidal anions with a quaternary ammonium cation act as efficient herbicides, which are under consideration to be used in the agriculture. In the present study, we used embryos of the zebrafish (Danio rerio) as a model to assess the toxic potential of ammonium-based ionic liquids for aquatic organisms. As we assumed interference of the partially hydrophobic ionic liquid cation with lipids, we investigated the adaptation response in the lipid composition of the zebrafish embryos, triggered by the ionic compound. Therefore, the impact of ammonium-based ionic liquids with different lengths of the alkyl chain ([C6,C6,C1,C1N][Br], [C8,C8,C1,C1N][Br]) on the phospholipid fatty acid (PLFA) profile of zebrafish embryos up to 72 hours post fertilization (hpf) was examined. Furthermore, the changes in the unsaturation index (UI) of PLFAs, as the sum parameter of membrane fluidity in eukaryotic cells, were presented. The PLFA’s UI in the zebrafish embryos upon exposure to quaternary ammonium salts was compared to the UI of the embryos upon exposure to nonionic 2,4-dichlorophenol, which has a similar hydrophobicity but is structurally different to [C8,C8,C1,C1N][Br]. It was shown that for ammonium-based ionic liquid precursors non-specific mode of action occurs and the toxic effect on lipid composition of zebrafish embryos can be well predicted based on chemical properties, like hydrophobicity. Furthermore, the changes in PLFAs, expressed by the UI, can be useful to study toxic effects of organic contamination. However, for zebrafish embryos, after ionic liquids and 2,4-DCP exposure, the changes were observed at high lethal concentrations, which caused the incidence of lethality of 30 and 50% of a group of test animals. PMID:29342167

Synthesis of graphene oxide-quaternary ammonium nanocomposite with synergistic antibacterial activity to promote infected wound healing.

PubMed

Liu, Tengfei; Liu, Yuqing; Liu, Menglong; Wang, Ying; He, Weifeng; Shi, Gaoqiang; Hu, Xiaohong; Zhan, Rixing; Luo, Gaoxing; Xing, Malcolm; Wu, Jun

2018-01-01

Bacterial infection is one of the most common complications in burn, trauma, and chronic refractory wounds and is an impediment to healing. The frequent occurrence of antimicrobial-resistant bacteria due to irrational application of antibiotics increases treatment cost and mortality. Graphene oxide (GO) has been generally reported to possess high antimicrobial activity against a wide range of bacteria in vitro . In this study, a graphene oxide-quaternary ammonium salt (GO-QAS) nanocomposite was synthesized and thoroughly investigated for synergistic antibacterial activity, underlying antibacterial mechanisms and biocompatibility in vitro and in vivo . The GO-QAS nanocomposite was synthesized through amidation reactions of carboxylic group end-capped QAS polymers with primary amine-decorated GO to achieve high QAS loading ratios on nanosheets. Next, we investigated the antibacterial activity and biocompatibility of GO-QAS in vitro and in vivo . GO-QAS exhibited synergistic antibacterial activity against bacteria through not only mechanical membrane perturbation, including wrapping, bacterial membrane insertion, and bacterial membrane perforation, but also oxidative stress induction. In addition, it was found that GO-QAS could eradicate multidrug-resistant bacteria more effectively than conventional antibiotics. The in vitro and in vivo toxicity tests indicated that GO-QAS did not exhibit obvious toxicity towards mammalian cells or organs at low concentrations. Notably, GO-QAS topically applied on infected wounds maintained highly efficient antibacterial activity and promoted infected wound healing in vivo . The GO-QAS nanocomposite exhibits excellent synergistic antibacterial activity and good biocompatibility both in vitro and in vivo . The antibacterial mechanisms involve both mechanical membrane perturbation and oxidative stress induction. In addition, GO-QAS accelerated the healing process of infected wounds by promoting re-epithelialization and granulation tissue formation. Overall, the results indicated that the GO-QAS nanocomposite could be applied as a promising antimicrobial agent for infected wound management and antibacterial wound dressing synthesis.

Integrated approach for investigating the durability of self-consolidating concrete to sulfate attack

NASA Astrophysics Data System (ADS)

Bassuoni, Mohamed Tamer F.

The growing use of self-consolidating concrete (SCC) in various infrastructure applications exposed to sulfate-rich environments necessitates conducting comprehensive research to evaluate its durability to external sulfate attack. Since the reliability and adequacy of standard sulfate immersion tests have been questioned, the current thesis introduced an integrated testing approach for assessing the durability of a wide scope of SCC mixtures to external sulfate attack. This testing approach involved progressive levels of complexity from single to multiple damage processes. A new series of sulfate attack tests involving multiple field-like parameters and combined damage mechanisms (various cations, controlled pH, wetting-drying, partial immersion, freezing-thawing, and cyclic cold-hot conditions with or without sustained flexural loading) were designed to evaluate the performance (suitability) of the SCC mixtures under various sulfate attack exposure scenarios. The main mixture design variables of SCC included the type of binder (single, binary, ternary and quaternary), air-entrainment, sand-to-aggregate mass ratio and hybrid fibre reinforcement. The comprehensive database and knowledge obtained from this research were used to develop smart models (fuzzy and neuro-fuzzy inference systems) based on artificial-intelligence to evaluate and predict the performance of the SCC mixtures under various sulfate attack exposure regimes implemented in this study. In full immersion tests involving high concentration sodium and magnesium sulfate solutions with controlled pH, the low penetrability of SCC was responsible for the high durability of specimens. Ternary and quaternary cementitious systems with or without limestone materials provided a passivating layer, with or without acid neutralization capacity, which protected SCC from severe damage in the aggressive sulfuric acid and ammonium sulfate solutions. In contrast to conclusions drawn from the sodium sulfate immersion tests, the combined sulfate attack tests captured performance risks and complex damage mechanisms associated with the SCC pore structure and constituent materials. Sodium sulfate attack with wetting-drying cycles and/or partial immersion under temperate-hot conditions synergistically caused significant damage to specimens, especially to quaternary cementitious systems having very fine pore structure, due to the build-up of salt crystals and sulfate reaction products. The deleterious effects of sulfate reaction products and salt crystallization on all cementitious systems were more severe under the combined sodium sulfate and freezing-thawing exposure, with a potential of sudden brittle failure. Laboratory experiments in the current work documented evidence for the occurrence of thaumasite sulfate attack (TSA) in cementitious systems containing limestone filler, not only under cold but also under temperate-hot conditions, which made specimens more vulnerable to damage in the combined sulfate attack tests. The field-like combined exposure of sodium sulfate, cyclic environments and flexural loading had synergistic effects on SCC specimens and caused the coexistence of multiple-complex degradation mechanisms (sulfate attack, TSA, stress-corrosion, salt crystallization, surface scaling and corrosion of surface steel fibres) depending on the mixture design variables. The current thesis demonstrates that relying only on sulfate immersion tests to evaluate the performance of cement-based materials can be risky. It also shows that linear and deterministic modeling of the performance of concrete structures under external sulfate attack is unrealistic. Fuzzy and adaptive-neuro fuzzy inference systems developed in the current thesis accurately and rationally predicted the serviceability, deterioration in engineering properties and time to failure of the SCC mixtures under the various sulfate attack exposure regimes adopted in the integrated testing approach. A durability evaluation factor from multiple performance criteria was created for the ammonium sulfate exposure. Environmental charts were developed to determine the level of aggression associated with sodium sulfate attack from temperature, RH and degree of wetting-drying expected in service. This novel modeling approach showed promising success in handling complex durability topics such as the sulfate attack of concrete, which involves non-linearity, ambiguity and interface with operator approximation. The current thesis provides needed fundamental knowledge on the durability of a wide scope of SCC mixtures to various sulfate attack exposure scenarios. It elucidates complex deterioration mechanisms and failure modes of cement-based materials under multi-mechanistic aging processes. It also proposes carefully engineered integrated sulfate attack tests that replicate various sulfate attack exposure regimes, which could be refined and standardized in the future. In addition, the current work introduced original knowledge-based smart models capable of handling uncertainty and providing reliable predictions for the behaviour of concrete under external sulfate attack. The models do not require conducting exhaustive laboratory experiments and/or making assumptions, thus facilitating the selection of optimum concrete mixtures for a specified exposure. Overall, this research should effectively contribute to the development of performance-based standards and specifications for, and improvement of durability-based design and life-cycle analysis of concrete structures subjected to external sulfate attack. Keywords. Sulfate attack, self-consolidating concrete, integrated testing, composite cements, air-entrainment, hybrid fibres, full immersion, cations, pH, wetting-drying, partial immersion, freezing-thawing, cyclic cold-hot conditions, flexural loading, thaumasite, salt crystallization, fuzzy, neuro-fuzzy, systems.

Minimal erosion of Arctic alpine topography during late Quaternary glaciation

NASA Astrophysics Data System (ADS)

Gjermundsen, Endre F.; Briner, Jason P.; Akçar, Naki; Foros, Jørn; Kubik, Peter W.; Salvigsen, Otto; Hormes, Anne

2015-10-01

The alpine topography observed in many mountainous regions is thought to have formed during repeated glaciations of the Quaternary period. Before this time, landscapes had much less relief. However, the spatial patterns and rates of Quaternary exhumation at high latitudes--where cold-based glaciers may protect rather than erode landscapes--are not fully quantified. Here we determine the exposure and burial histories of rock samples from eight summits of steep alpine peaks in northwestern Svalbard (79.5° N) using analyses of 10Be and 26Al concentrations. We find that the summits have been preserved for at least the past one million years. The antiquity of Svalbard’s alpine landscape is supported by the preservation of sediments older than one million years along a fjord valley, which suggests that both mountain summits and low-elevation landscapes experienced very low erosion rates over the past million years. Our findings support the establishment of northwestern Svalbard’s alpine topography during the early Quaternary. We suggest that, as the Quaternary ice age progressed, glacial erosion in the Arctic became inefficient and confined to ice streams, and high-relief alpine landscapes were preserved by minimally erosive glacier armour.

The influence of climate on species distribution over time and space during the late Quaternary

NASA Astrophysics Data System (ADS)

Carotenuto, F.; Di Febbraro, M.; Melchionna, M.; Castiglione, S.; Saggese, F.; Serio, C.; Mondanaro, A.; Passaro, F.; Loy, A.; Raia, P.

2016-10-01

Understanding the effect of climate on the composition of communities and its change over time and space is one of the major aims in ecology and paleoecology. Herein, we tackled on this issue by studying late Quaternary large mammal paleocommunities of Eurasia. The late Quaternary was a period of strong environmental instability, especially characterized by the occurrence of the last glacial maximum (LGM). We used community phylogenetics and joint species distribution models in order to understand the factors determining paleocommunity composition in the late Quaternary. Our results support the existence of strong climatic selection operating on the LGM fauna, both through the disappearance of warm-adapted species such as Elephas antiquus, Hippopothamus amphibious, and Stephanorhinus hemitoechus, and by setting the stage for the existence of a community characterized by cold-adapted large mammals. Patterns of abundance in the fossil record, co-occurrence between species pairs, and the extent of climatic forcing on faunal composition, differ between paleocommunities, but not between extinct and extant species, which is consistent with the idea that climate change, rather than the presence of humans, exerted a major effect on the survival of the late Quaternary megafauna.

Analysis of residual products in triethylbenzylammonium chloride by HPLC. Study of the retention mechanism.

PubMed

Prieto-Blanco, M C; López-Mahía, P; Prada-Rodríguez, D

2006-04-01

The control of industrial products for minimization of their impact on the environment and human health requires the development of specific analysis methods. Information provided by these methods about toxic components, by-products, and other derivatives may also be useful to reduce the possible impact of industrial products. The studied compound in this paper, triethylbenzylammonium chloride (TEBA), is mainly used in industrial synthesis. This quaternary compound and its residual products coming from quaternization reaction (benzyl chloride, benzaldehyde, and benzyl alcohol) are analyzed by HPLC. The separation is based on control of the silanophilic contribution to TEBA retention because of the quaternary nature of this compound. The effect of the three buffers (sodium acetate, ammonium acetate, and sodium formate) and their concentrations in the chromatographic behavior of the quaternary compound is examined. The buffer cation and anion regulate TEBA retention. Also, the concentration of the quaternary compound is another parameter that had influence in some aspects of its chromatographic behavior (e.g., retention and symmetry). The proposed method is applied to TEBA synthesis along, with the formation and removal of impurities with the results compared with those obtained for the quaternary compound benzalkonium chloride.

A Systematic Investigation of Quaternary Ammonium Ions as Asymmetric Phase Transfer Catalysts. Synthesis of Catalyst Libraries and Evaluation of Catalyst Activity

PubMed Central

Denmark, Scott E.; Gould, Nathan D.; Wolf, Larry M.

2011-01-01

Despite over three decades of research into asymmetric phase transfer catalysis (APTC), a fundamental understanding of the factors that affect the rate and stereoselectivity of this important process are still obscure. This paper describes the initial stages of a long-term program aimed at elucidating the physical organic foundations of APTC employing a chemoinformatic analysis of the alkylation of a protected glycine imine with a libraries of enantiomerically enriched quaternary ammonium ions. The synthesis of the quaternary ammonium ions follows a diversity oriented approach wherein the tandem inter[4+2]/intra[3+2] cycloaddition of nitroalkenes serves as the key transformation. A two part synthetic strategy comprised of: (1) preparation of enantioenriched scaffolds and (2) development of parallel synthesis procedures is described. The strategy allows for the facile introduction of four variable groups in the vicinity of a stereogenic quaternary ammonium ion. The quaternary ammonium ions exhibited a wide range of activity and to a lesser degree enantioselectivity. Catalyst activity and selectivity are rationalized in a qualitative way based on the effective positive potential of the ammonium ion. PMID:21446721

Bactericidal Specificity and Resistance Profile of Poly(Quaternary Ammonium) Polymers and Protein-Poly(Quaternary Ammonium) Conjugates.

PubMed

Ji, Weihang; Koepsel, Richard R; Murata, Hironobu; Zadan, Sawyer; Campbell, Alan S; Russell, Alan J

2017-08-14

Antibacterial polymers are potentially powerful biocides that can destroy bacteria on contact. Debate in the literature has surrounded the mechanism of action of polymeric biocides and the propensity for bacteria to develop resistance to them. There has been particular interest in whether surfaces with covalently coupled polymeric biocides have the same mechanism of action and resistance profile as similar soluble polymeric biocides. We designed and synthesized a series of poly(quaternary ammonium) polymers, with tailorable molecular structures and architectures, to engineer their antibacterial specificity and their ability to delay the development of bacterial resistance. These linear poly(quaternary ammonium) homopolymers and block copolymers, generated using atom transfer radical polymerization, had structure-dependent antibacterial specificity toward Gram positive and negative bacterial species. When single block copolymers contained two polymer segments of differing antibacterial specificity, the polymer combined the specificities of its two components. Nanoparticulate human serum albumin-poly(quaternary ammonium) conjugates of these same polymers, synthesized via "grafting from" atom transfer radical polymerization, were strongly biocidal and also exhibited a marked decrease in the rate of bacterial resistance development relative to linear polymers. These protein-biocide conjugates mimicked the behavior of surface-presented polycationic biocides rather than their nonproteinaceous counterparts.

87Sr/86Sr in Gypsic Relict Soils and Paleosols of Hyperarid Settings as a Paleoaltitude Proxy: Results for Northern Chile (19.5-21.7°S)

NASA Astrophysics Data System (ADS)

Jordan, T. E.; Cosentino, N. J.

2014-12-01

We have developed a new altimeter proxy based on the 87Sr/86Sr ratio of surficial accumulations of salts in hyperarid settings. Under hyperarid conditions like in the Andean forearc in northern Chile at altitudes below ~3000 m.a.s.l., gypsum and other soluble salts form saline soils. The altimeter is based on the first-order topographic control on the extent of inland incursion of fog-transported marine aerosols derived from the Pacific Ocean. Once this fog is evaporated it deposits calcium sulfates with a marine 87Sr/86Sr signal. At positions in the landscape not reached by marine aerosols, calcium sulfates have no marine source, except by eolian reworking, and have a lower 87Sr/86Sr. 87Sr/86Sr values for Holocene accumulations of salts show a bimodal distribution: high values between 225-1075 m.a.s.l. (0.70807 ± 0.00004) and low values below and above those altitude thresholds (0.70746 ± 0.00010). We sampled dated gypsic relict soils and Gypsisols to study post-5 Ma surface height evolution using this method, after correcting for changes in the altitudinal structure of the paleo-fog zone with time. Locations spanning ~250 km strike-parallel distance within the forearc and at elevations between 450-1650 m.a.s.l. display moderate amounts of altitudinal change during the Pliocene, Pleistocene and Quaternary. Site results include two in the northern zone (19.5ºS and 19.65ºS) that experienced maximum net surface uplifts of ~350 m and ~600 m since 2.5 ± 0.5 Ma and ~2.6 Ma, respectively. Locations at ~21.4°S display an estimated minimum net decline in altitude of ~250 m since 3.4 ± 1.1 Ma and ~200 m since 1.1 ± 0.4 Ma. These constraints will shed light on the geodynamic processes responsible for surface elevation change, by acting as boundary conditions to numerical models of the Andean forearc.

Catalytic Enantioselective Synthesis of Quaternary Carbon Stereocenters

PubMed Central

Quasdorf, Kyle W.; Overman, Larry E.

2015-01-01

Preface Quaternary carbon stereocenters–carbon atoms to which four distinct carbon substituents are attached–are common features of molecules found in nature. However, prior to recent advances in chemical catalysis, there were few methods available for constructing single stereoisomers of this important structural motif. Here we discuss the many catalytic enantioselective reactions developed during the past decade for synthesizing organic molecules containing such carbon atoms. This progress now makes it possible to selectively incorporate quaternary stereocenters in many high-value organic molecules for use in medicine, agriculture, and other areas. PMID:25503231

Thermodynamic Description of the Quaternary Ag-Bi-Cu-Sn System

NASA Astrophysics Data System (ADS)

Gierlotka, Wojciech

2018-01-01

Lead-free soldering is an important part of electronic devices production. New lead-free solders that replace classical Sn-37Pb solder are still under development. Thermodynamic modeling makes the development process faster, cheaper and more environmentally friendly due to predictions of phases stabilities and phases transformations. In this work, the thermodynamic description of quaternary Ag-Bi-Cu-Sn system is presented. The thermodynamic assessment of promising lead-free quaternary solder was prepared using the Calphad approach. A good agreement between available experimental data and calculation was found.

Quaternary ammonium promoted ultra selective and sensitive fluorescence detection of fluoride ion in water and living cells.

PubMed

Li, Long; Ji, Yuzhuo; Tang, Xinjing

2014-10-21

Highly selective and sensitive fluorescent probes with a quaternary ammonium moiety have been rationally designed and developed for fast and sensitive fluorescence detection of fluoride ion (F(-) from NaF, not TBAF) in aqueous solution and living cells. With the sequestration effect of quaternary ammonium, the detection time was less than 2 min and the detection limit of fluoride ion was as low as 0.57 ppm that is among the lowest detection limits in aqueous solutions of many fluoride fluorescence probes in the literature.

Spatiotemporal analysis of Quaternary normal faults in the Northern Rocky Mountains, USA

NASA Astrophysics Data System (ADS)

Davarpanah, A.; Babaie, H. A.; Reed, P.

2010-12-01

The mid-Tertiary Basin-and-Range extensional tectonic event developed most of the normal faults that bound the ranges in the northern Rocky Mountains within Montana, Wyoming, and Idaho. The interaction of the thermally induced stress field of the Yellowstone hot spot with the existing Basin-and-Range fault blocks, during the last 15 my, has produced a new, spatially and temporally variable system of normal faults in these areas. The orientation and spatial distribution of the trace of these hot-spot induced normal faults, relative to earlier Basin-and-Range faults, have significant implications for the effect of the temporally varying and spatially propagating thermal dome on the growth of new hot spot related normal faults and reactivation of existing Basin-and-Range faults. Digitally enhanced LANDSAT 7 Enhanced Thematic Mapper Plus (ETM+) and Landsat 4 and 5 Thematic Mapper (TM) bands, with spatial resolution of 30 m, combined with analytical GIS and geological techniques helped in determining and analyzing the lineaments and traces of the Quaternary, thermally-induced normal faults in the study area. Applying the color composite (CC) image enhancement technique, the combination of bands 3, 2 and 1 of the ETM+ and TM images was chosen as the best statistical choice to create a color composite for lineament identification. The spatiotemporal analysis of the Quaternary normal faults produces significant information on the structural style, timing, spatial variation, spatial density, and frequency of the faults. The seismic Quaternary normal faults, in the whole study area, are divided, based on their age, into four specific sets, which from oldest to youngest include: Quaternary (>1.6 Ma), middle and late Quaternary (>750 ka), latest Quaternary (>15 ka), and the last 150 years. A density map for the Quaternary faults reveals that most active faults are near the current Yellowstone National Park area (YNP), where most seismically active faults, in the past 1.6 my, are located. The GIS based autocorrelation method, applied to the trace orientation, length, frequency, and spatial distribution for each age-defined fault set, revealed spatial homogeneity for each specific set. The results of the method of Moran`sI and Geary`s C show no spatial autocorrelation among the trend of the fault traces and their location. Our results suggest that while lineaments of similar age define a clustered pattern in each domain, the overall distribution pattern of lineaments with different ages seems to be non-uniform (random). The directional distribution analysis reveals a distinct range of variation for fault traces of different ages (i.e., some displaying ellipsis behavior). Among the Quaternary normal fault sets, the youngest lineament set (i.e., last 150 years) defines the greatest ellipticity (eccentricity) and the least lineaments distribution variation. The frequency rose diagram for the entire Quaternary normal faults, shows four major modes (around 360o, 330o, 300o, and 270o), and two minor modes (around 235 and 205).

Coupling Geophysical, Geotechnical and Stratigraphic Data to Interpret the Genesis of Mega-Scale-Glacial-Lineations on the Yermak Plateau, Arctic Ocean

NASA Astrophysics Data System (ADS)

O'Regan, M. A.; Jakobsson, M.; Kirchner, N.; Dowdeswell, J. A.; Hogan, K.

2010-12-01

The recent collection and analysis of multi-beam bathymetry data has revealed Mega-Scale Glacial Lineations (MSGL) in up to 600 m present water depth on the Yermak Plateau (Dowdeswell et al., 2010; Jakobsson et al., 2010). This evidence for large-scale ice grounding in the region supports previous interpretations from side-scan sonar, high-resolution subbottom and multi-channel seismic data. Detailed integration with regional subbottom data illustrates that the formation of the MSGL occurred in the late Quaternary, around MIS6. This event is distinct from a middle Quaternary ice grounding in the same region, that was first recognized by the transition into heavily overconsolidated sediments at ~20 mbsf at Ocean Drilling Program Site 910. While the middle Quaternary ice grounding left an easily recognizable imprint on the geotechnical properties of the sediments, the imprint from the late Quaternary event is far subtler, and not formerly recognized by analysis of sediments from Site 910. Furthermore, stratigraphic information indicates that neither event was associated with significant erosion, implying that the observed stress state of the sediments arose from ice-loading. Coupled with the orientation of the late Quaternary MSGL, the available evidence argues against an active ice-stream being responsible for their formation, and that they were more likely formed by a very large tabular iceberg traversing the ridge. This lends considerable support to the argument that MSGL-like features are not exclusively associated with fast flowing ice-streams. References Jakobsson, M., et al., An Arctic Ocean iceshelf during MIS 6 constrained by new geophysical and geological data. Quaternary Science Reviews (2010), doi:10.1016/j.quascirev.2010.03.015. Dowdeswell, J. A., et al., High-resolution geophysical observations of the Yermak Plateau and northern Svalbard margin: implications for ice-sheet grounding and deep-keeled icebergs. Quaternary Science Reviews (2010), doi:10.1016/j.quascirev.2010.06.002

Map and data for Quaternary faults and folds in Washington state

USGS Publications Warehouse

Lidke, David J.; Johnson, Samuel Y.; McCrory, Patricia A.; Personius, Stephen F.; Nelson, Alan R.; Dart, Richard L.; Bradley, Lee-Ann; Haller, Kathleen M.; Machette, Michael N.

2004-01-01

The map shows faults and folds in Washington State that exhibit evidence of Quaternary deformation and includes data on timing of most recent movement, sense of movement, slip rate, and continuity of surface expression.

A solution-processed quaternary oxide system obtained at low-temperature using a vertical diffusion technique

PubMed Central

Yoon, Seokhyun; Kim, Si Joon; Tak, Young Jun; Kim, Hyun Jae

2017-01-01

We report a method for fabricating solution-processed quaternary In-Ga-Zn-O (IGZO) thin-film transistors (TFTs) at low annealing temperatures using a vertical diffusion technique (VDT). The VDT is a deposition process for spin-coating binary and ternary oxide layers consecutively and annealing at once. With the VDT, uniform and dense quaternary oxide layers were fabricated at lower temperatures (280 °C). Compared to conventional IGZO and ternary In-Zn-O (IZO) thin films, VDT IGZO thin film had higher density of the metal-oxide bonds and lower density of the oxygen vacancies. The field-effect mobility of VDT IGZO TFT increased three times with an improved stability under positive bias stress than IZO TFT due to the reduction in oxygen vacancies. Therefore, the VDT process is a simple method that reduces the processing temperature without any additional treatment for quaternary oxide semiconductors with uniform layers. PMID:28230088

A solution-processed quaternary oxide system obtained at low-temperature using a vertical diffusion technique

NASA Astrophysics Data System (ADS)

Yoon, Seokhyun; Kim, Si Joon; Tak, Young Jun; Kim, Hyun Jae

2017-02-01

We report a method for fabricating solution-processed quaternary In-Ga-Zn-O (IGZO) thin-film transistors (TFTs) at low annealing temperatures using a vertical diffusion technique (VDT). The VDT is a deposition process for spin-coating binary and ternary oxide layers consecutively and annealing at once. With the VDT, uniform and dense quaternary oxide layers were fabricated at lower temperatures (280 °C). Compared to conventional IGZO and ternary In-Zn-O (IZO) thin films, VDT IGZO thin film had higher density of the metal-oxide bonds and lower density of the oxygen vacancies. The field-effect mobility of VDT IGZO TFT increased three times with an improved stability under positive bias stress than IZO TFT due to the reduction in oxygen vacancies. Therefore, the VDT process is a simple method that reduces the processing temperature without any additional treatment for quaternary oxide semiconductors with uniform layers.

Mössbauer and XRD study of novel quaternary Sn-Fe-Co-Ni electroplated alloy

NASA Astrophysics Data System (ADS)

Kuzmann, E.; Sziráki, L.; Stichleutner, S.; Homonnay, Z.; Lak, G. B.; El-Sharif, M.; Chisholm, C. U.

2017-11-01

Constant current electrochemical deposition technique was used to obtain quaternary alloys of Sn-Fe-Co-Ni from a gluconate electrolyte, which to date have not been reported in the literature. For the characterization of electroplated alloys, 57Fe and 119Sn Conversion Electron Mössbauer Spectroscopy (CEMS), XRD and SEM/EDAX were used. XRD revealed the amorphous character of the novel Sn-Fe-Co-Ni electrodeposited alloys. 57Fe Mössbauer spectrum of quaternary deposit with composition of 37.0 at% Sn, 38.8 at% Fe, 16.8 at% Co and 7.4 at% Ni displayed a magnetically split sextet (B = 28.9T) with broad lines typical of iron bearing ferromagnetic amorphous alloys. Magnetically split 119Sn spectra reflecting a transferred hyperfine field (B = 2.3T) were also observed. New quaternary Sn-Fe-Co-Ni alloys were successfully prepared.

A solution-processed quaternary oxide system obtained at low-temperature using a vertical diffusion technique.

PubMed

Yoon, Seokhyun; Kim, Si Joon; Tak, Young Jun; Kim, Hyun Jae

2017-02-23

We report a method for fabricating solution-processed quaternary In-Ga-Zn-O (IGZO) thin-film transistors (TFTs) at low annealing temperatures using a vertical diffusion technique (VDT). The VDT is a deposition process for spin-coating binary and ternary oxide layers consecutively and annealing at once. With the VDT, uniform and dense quaternary oxide layers were fabricated at lower temperatures (280 °C). Compared to conventional IGZO and ternary In-Zn-O (IZO) thin films, VDT IGZO thin film had higher density of the metal-oxide bonds and lower density of the oxygen vacancies. The field-effect mobility of VDT IGZO TFT increased three times with an improved stability under positive bias stress than IZO TFT due to the reduction in oxygen vacancies. Therefore, the VDT process is a simple method that reduces the processing temperature without any additional treatment for quaternary oxide semiconductors with uniform layers.

Principles of assembly reveal a periodic table of protein complexes.

PubMed

Ahnert, Sebastian E; Marsh, Joseph A; Hernández, Helena; Robinson, Carol V; Teichmann, Sarah A

2015-12-11

Structural insights into protein complexes have had a broad impact on our understanding of biological function and evolution. In this work, we sought a comprehensive understanding of the general principles underlying quaternary structure organization in protein complexes. We first examined the fundamental steps by which protein complexes can assemble, using experimental and structure-based characterization of assembly pathways. Most assembly transitions can be classified into three basic types, which can then be used to exhaustively enumerate a large set of possible quaternary structure topologies. These topologies, which include the vast majority of observed protein complex structures, enable a natural organization of protein complexes into a periodic table. On the basis of this table, we can accurately predict the expected frequencies of quaternary structure topologies, including those not yet observed. These results have important implications for quaternary structure prediction, modeling, and engineering. Copyright © 2015, American Association for the Advancement of Science.

Tertiary and Quaternary Research with Remote Sensing Methods

NASA Technical Reports Server (NTRS)

Conel, J. E.

1985-01-01

Problems encountered in mapping the Quaternary section of the Wind River Region using remote sensing methods are discussed. Analysis of the stratigraphic section is a fundamental aspect of the geologic study of sedimentary basins. Stratigraphic analysis of post-Cretaceous rocks in the Wind River Basin encounters problems of a distinctly different character from those involved in studying the pre-Cretaceous section. The interior of the basin is predominantly covered by Tertiary and Quaternary sediments. These rocks, except on the basin margin to the north, are mostly flat lying or gently dipping. The Tertiary section consists of sandstones, siltstones, and tuffaceous sediments, some variegated, but in general poorly bedded and of great lithologic similarity. The Quaternary sediments consist of terrace, fan, and debris tongue deposits, unconsolidated alluvium occupying the bottoms of modern watercourses, deposits of eolian origin and tufa. Terrace and fan deposits are compositionally diverse and reflect the lithologic diversity of the source terranes.

Antiplaque and antigingivitis toothpastes.

PubMed

Sanz, Mariano; Serrano, Jorge; Iniesta, Margarita; Santa Cruz, Isabel; Herrera, David

2013-01-01

Dentifrices are a general term used to describe preparations that are used together with a toothbrush with the purpose to clean and/or polish the teeth. Active toothpastes were first formulated in the 1950s and included ingredients such as urea, enzymes, ammonium phosphate, sodium lauryl sarcosinate and stannous fluoride. Later, therapeutic agents were included. Today's toothpastes have two objectives: to help the toothbrush in cleaning the tooth surface and to provide a therapeutic effect. The therapeutic effect may have an antiplaque or anti-inflammatory basis when the nature of the agents is antimicrobial. Plaque inhibitory and antiplaque activity of toothpastes used for chemical plaque control is evaluated in distinct consecutive stages, the last being home use randomized clinical trials of at least 6 months' duration. In this chapter, the scientific evidence supporting the use of the most common antiplaque agents, included in toothpaste formulations, is reviewed, with a special emphasis on 6-month clinical trials, and systematic reviews with meta-analyses of the mentioned studies. Among the active agents, the following have been included in toothpastes: enzymes, amine alcohols, herbal or natural products, triclosan, bisbiguanides (chlorhexidine), quaternary ammonium compounds (cetylpyridinium chloride) and different metal salts (zinc salts, stannous fluoride, stannous fluoride with amine fluoride). Dentifrices are the ideal vehicles for any active ingredient used as an oral health preventive measure since they are used in combination with toothbrushing, which is the most frequently employed oral hygiene method. The most important indications of dentifrices with active ingredients are associated with long-term use to prevent bacterial biofilm formation, mostly in gingivitis patients or in patients on supportive periodontal therapy. Copyright © 2013 S. Karger AG, Basel.

Synthesis and pharmacological effects of the enantiomers of the N-phenethyl analogues of the ortho and para e- and f-oxide-bridged phenylmorphans‡

PubMed Central

Zezula, Josef; Singer, Lisa; Przybyl, Anna K.; Hashimoto, Akihiro; Dersch, Christina M.; Rothman, Richard B.; Deschamps, Jeffrey; Lee, Yong Sok; Jacobson, Arthur E.; Rice, Kenner C.

2008-01-01

The N-phenethyl analogues of (1R*,4aR*,9aS*)-2-phenethyl-1,3,4,9a-tetrahydro-2H-1,4a-propanobenzofuro[2,3-c]pyridin-6-ol and 8-ol and (1R*,4aR*,9aR*)-2-phenethyl-1,3,4,9a-tetrahydro-2H-1,4a-propanobenzofuro[2.3-c]pyridin-6-ol and 8-ol, the ortho- (43) and para-hydroxy e- (20), and f-oxide-bridged 5-phenylmorphans (53 and 26) were prepared in racemic and enantiomerically pure forms from a common precursor, the quaternary salt 12. Optical resolutions were accomplished by salt formation with suitable enantiomerically pure chiral acids or by preparative HPLC on a chiral support. The N-phenethyl (−)- para-e enantiomer (1S,4aS,9aR-(−)-20) was found to be a μ-opioid agonist with morphine-like antinociceptive activity in a mouse assay. In contrast, the N-phenethyl (−)-ortho-f enantiomer (1R,4aR,9aR-(−)-53) had good affinity for the μ-opioid receptor (Ki = 7 nM) and was found to be a μ-antagonist both in the [35S]GTP-γ-S assay and in vivo. The molecular structures of these rigid enantiomers were energy minimized with density functional theory at the level B3LYP/6-31G* level, and then overlayed on a known potent μ-agonist. This superposition study suggests that the agonist activity of the oxide-bridged 5-phenylmorphans can be attributed to formation of a seven membered ring that is hypothesized to facilitate a proton transfer from the protonated nitrogen to a proton acceptor in the μ-opioid receptor. PMID:18688479

DOE Office of Scientific and Technical Information (OSTI.GOV)

Landauer, Alexander K.; Barnhill, William C.; Qu, Jun

Here we examine the elasticity, hardness, and resistance-to-plastic-deformation (P/S 2) measured via nanoindentation of several tribofilms and correlates these properties to friction and wear behavior. The tribofilms were generated by ball-on-plate reciprocating sliding lubricated by a base oil containing an ionic liquid, phosphonium-organophosphate or ammonium-organophosphate, zinc dialkyldithiophosphate (ZDDP), or combination of IL and ZDDP. Nanoindentation was conducted at room and elevated temperatures. While there seems little correlation between the tribofilm hardness and tribological behavior, a higher modulus generally leads to better friction and wear performance. Interestingly, a lower P/S 2 ratio tends to reduce friction and improve wear protection, whichmore » is in an opposite trend as reported for bulk materials. Ultimately, this is likely attributable to the dynamic, self-healing characteristics of tribofilms.« less

Distinguishing Aspartic and Isoaspartic Acids in Peptides by Several Mass Spectrometric Fragmentation Methods

NASA Astrophysics Data System (ADS)

DeGraan-Weber, Nick; Zhang, Jun; Reilly, James P.

2016-12-01

Six ion fragmentation techniques that can distinguish aspartic acid from its isomer, isoaspartic acid, were compared. MALDI post-source decay (PSD), MALDI 157 nm photodissociation, tris(2,4,6-trimethoxyphenyl)phosphonium bromide (TMPP) charge tagging in PSD and photodissociation, ESI collision-induced dissociation (CID), electron transfer dissociation (ETD), and free-radical initiated peptide sequencing (FRIPS) with CID were applied to peptides containing either aspartic or isoaspartic acid. Diagnostic ions, such as the y-46 and b+H2O, are present in PSD, photodissociation, and charge tagging. c•+57 and z-57 ions are observed in ETD and FRIPS experiments. For some molecules, aspartic and isoaspartic acid yield ion fragments with significantly different intensities. ETD and charge tagging appear to be most effective at distinguishing these residues.

Fundamentals of Polymer Gel Dosimeters

NASA Astrophysics Data System (ADS)

McAuley, Kim B.

2006-12-01

The recent literature on polymer gel dosimetry contains application papers and basic experimental studies involving polymethacrylic-acid-based and polyacrylamide-based gel dosimeters. The basic studies assess the relative merits of these two most commonly used dosimeters, and explore the effects of tetrakis hydroxymethyl phosphonium chloride (THPC) antioxidant on dosimeter performance. Polymer gel dosimeters that contain THPC or other oxygen scavengers are called normoxic dosimeters, because they can be prepared under normal atmospheric conditions, rather than in a glove box that excludes oxygen. In this review, an effort is made to explain some of the underlying chemical phenomena that affect dosimeter performance using THPC, and that lead to differences in behaviour between dosimeters made using the two types of monomer systems. Progress on the development of new more effective and less toxic dosimeters is also reported.

Missing in Action? Evaluating the Putative Absence of Impacts by Large Asteroids and Comets during the Quaternary Period

NASA Astrophysics Data System (ADS)

Masse, W.; Weaver, R.; Abbott, D.; Gusiakov, V.; Bryant, E.

The Quaternary period represents the interval of oscillating climatic extremes (glacial and interglacial periods) beginning about 2.6 million years ago to the present. Based on modeling by the Near Earth Object (NEO) community of planetary scientists, the known and validated record of Quaternary impact on Earth by comets and asteroids is seemingly depauperate in terms of larger impactors of 10,000+ Mt (roughly equal to or larger than about 500 m in diameter). Modeling suggests that an average of between 2-3 and perhaps as many as 5 globally catastrophic (ca. 1,000,000+ Mt) impacts by asteroids and comets could have occurred on Earth during this period of time, each having catastrophic regional environmental effects and moderate to severe continental and global effects. A slightly larger number of substantive but somewhat less than globally catastrophic impacts in the 10,000-100,000 Mt range would also be predicted to have occurred during the Quaternary. However, databases of validated impact structures on Earth, contain only two examples of Quaternary period impacts in the 10,000-100,000 Mt range (Zhamanshin, Bosumtwi), dating to around a million years ago, while no examples of Quaternary period globally catastrophic impact structures have been yet identified. In addition, all of the 27 validated Quaternary period impact structures are terrestrial--no Quaternary period oceanic impacts have been yet validated. Two likely globally catastrophic probable oceanic impacts events, Eltanin (ca. 1,000,000 Mt at around 2.5 mya), and that associated with the Australasian tektite strewn field (> 1,000,000 Mt at around 0.8 mya), are known due to their debris fields for which craters have not yet been identified and validated. These and the 8-km diameter Bolivian Iturralde candidate impact structure (ca. 10,000 Mt at around 20 kya) round out our list of likely large Quaternary impact structures. This suggests that one or more Quaternary period globally catastrophic impacts and several events in the 10,000-100,000 Mt range occurred in oceanic settings and have not yet been identified. At issue here is the default position of the NEO community that no large impacts have occurred during the past 15,000 years and that there is little evidence for human death by impacts during the past 5000 years of recorded history. This bias, deriving largely from reliance on stochastic models and by selectively ignoring physical, anthropological, and archaeological evidence in support of such impacts, is apparent in the messages being given to the media and general public, and in the general lack of grant support and other assistance to scientists and scholars wishing to conduct fieldwork on impacts that may date to the past 15,000 years. Such a position has a chilling effect on what should otherwise be an important arena of inquiry into the risks and effects of cosmic impact on human society. It potentially limits advancement in our understanding of the recent record and flux of cosmic impact, and diverts attention away from significant research questions such as the possible role of impact in Quaternary period climate change and biological and cultural evolution and process. LA-UR-07-2526.

Quaternary tectonic evolution of the Pamir-Tian Shan convergence zone, Northwest China

NASA Astrophysics Data System (ADS)

Thompson Jobe, Jessica Ann; Li, Tao; Chen, Jie; Burbank, Douglas W.; Bufe, Aaron

2017-12-01

The Pamir-Tian Shan collision zone in the western Tarim Basin, northwest China, formed from rapid and ongoing convergence in response to the Indo-Eurasian collision. The arid landscape preserves suites of fluvial terraces crossing structures active since the late Neogene that create fault and fold scarps recording Quaternary deformation. Using geologic and geomorphic mapping, differential GPS surveys of deformed terraces, and optically stimulated luminescence dating, we create a synthesis of the active structures that delineate the timing, rate, and migration of Quaternary deformation during ongoing convergence. New deformation rates on eight faults and folds, when combined with previous studies, highlight the spatial and temporal patterns of deformation within the Pamir-Tian Shan convergence zone during the Quaternary. Terraces spanning 130 to 8 ka record deformation rates between 0.1 and 5.6 mm/yr on individual structures. In the westernmost Tarim Basin, where the Pamir and Tian Shan are already juxtaposed, the fastest rates occur on actively deforming structures at the interface of the Pamir-Tian Shan orogens. Farther east, as the separation between the Pamir-Tian Shan orogens increases, the deformation has not been concentrated on a single structure, but rather has been concurrently distributed across a zone of faults and folds in the Kashi-Atushi fold-and-thrust belt and along the NE Pamir margin, where shortening rates vary on individual structures during the Quaternary. Although numerous structures accommodate the shortening and the locus of deformation shifts during the Quaternary, the total shortening across the western Tarim Basin has remained steady and approximately matches the current geodetic rate of 6-9 mm/yr.

Diversification dynamics, species sorting, and changes in the functional diversity of marine benthic gastropods during the Pliocene-Quaternary at temperate western South America.

PubMed

Rivadeneira, Marcelo M; Nielsen, Sven N

2017-01-01

Functional diversity based on species traits is a powerful tool to investigate how changes in species richness and composition affect ecosystem functioning. However, studies aimed at understanding changes in functional diversity over large temporal and spatial scales are still scant. Here we evaluate the combined effect of diversification and species sorting on functional diversity of fossil marine gastropods during the Pliocene-Quaternary transition in the Pacific coast of South America. We analyzed a total of 172 species in 29 Pliocene and 97 Quaternary sites. Each species was characterized according to six functional traits: body size, feeding type, mobility, attachment, life-habit, and larval mode. Functional diversity was estimated according to four indexes (functional richness, evenness, divergence and dispersion) based on functional traits measured. Extrapolated species richness showed a slight yet not significant decrease from the Pliocene to the Quaternary despite the fact that a large faunal turnover took place; furthermore, a large extinction of Pliocene species (61-76%) was followed by a high pulse of appearances (49-56%) during the Quaternary. Three out of four indices of functional diversity (evenness, divergence and dispersion) increased significantly towards the Quaternary which is more than expected under a random turnover of species. The increase in functional diversity is associated with a loss of large-sized carnivore forms, which tended to be replaced by small-sized grazers. Hence, this trait-selective species turnover, even in the absence of significant changes in species richness, likely had a large effect and has shaped the functional diversity of present-day assemblages.

Microbial life in continental salt pan sediments and their response to climate variability in Northern South Africa

NASA Astrophysics Data System (ADS)

Genderjahn, Steffi; Mangelsdorf, Kai; Alawi, Mashal; Belz, Lukas; Kallmeyer, Jens; Wagner, Dirk

2016-04-01

The environmental history of southwestern African mainland is largely unknown. Since there are no lacustrine systems with constant water coverage in this area, we investigated a continental salt pan as a terrestrial geoarchive with the potential to preserve climate signals. Within the frame of the research project "GeoArchives" (part of the SPACES program, funded by the German Federal Ministry of Education and Research, BMBF) we aimed to reconstruct climate variabilities during the late Pleistocene to Holocene. The presented study is focused on variations within the microbial community structure and abundance of key organisms in a salt pan with special regards to sediment age and geochemical parameters. A combined approach of a 16S rDNA-based quantification method and lipid biomarker analysis was used to demonstrate the response of the microbial communities with respect to environmental changes. The phospholipid derived fatty acids (PLFAs) in sedimentary deposits are characteristic markers for living Bacteria, whereby their side chain represents a fingerprint of the community structure on a broad taxonomic level. Archaeol and isoprenoid glycerol dialkyl glycerol tetraethers (iGDGTs) were used as characteristic makers for Archaea whereas branched GDGTs (brGDGTs) are typical biomarkers for Bacteria. In contrast to PLFAs, they represent dead microbial biomass and thus the past microbial communities in older sediments, since they are already partly degraded. Samples from the Witpan, located in the northwest of South Africa and representing a depths profile from the Late Pleistocene to Holocene, were gathered. Despite the extreme environment with rather low TOC values, restricted availability of water and high salt concentration markers for Bacteria and Archaea were observed. A series of saturated, branched and unsaturated PLFAs were identified. The diversity and concentration of PLFAs were highest in the top layers (up to 30000 ng gsed-1, 0-10 cm) and characteristic markers for cyanobacteria were most abundant. The community composition changed with depths and both the copy numbers of 16S rDNA genes of bacteria (varied from 102 to 105 cell gsed-1) and the amount of PLFAs (up to 3000 ng gsed-1) reflected a low abundance of microorganisms despite increasing feedstock in deeper sediments. Thus, the actual salt pan microbial community is mainly located in the top layers and decreases with depth. In contrast archaeol and GDGTs increased at the transition from Holocene to deeper Late Pleistocene sediments (from 40 up to 3400 ng gsed-1) indicating a higher past microbial abundance during the Late Pleistocene. The increase of GDGTs, TOC, acetate and formate suggested a higher supply of organic matter and a higher microbial activity in this period. Therefore, we assumed an increased precipitation during the Late Pleistocene compared to the arid Holocene in southwestern Africa. We could show the potential of continental salt pans to preserve climate signals during deposition and we demonstrated their potential as a Late Quaternary geoarchive by means of lipid biomarker studies. To describe the environmental habitat, a detailed analysis of diversity and abundance of microorganisms using Next Generation Sequencing is planned.

Estimation of F-3 and F-4 knock-limited performance ratings for ternary and quaternary blends containing triptane or other high-antiknock aviation-fuel blending agents

NASA Technical Reports Server (NTRS)

Barnett, Henry C

1948-01-01

Charts are presented that permit the estimation of F-3 and F-4 knock-limited performance ratings for certain ternary and quaternary fuel blends. Ratings for various ternary and quaternary blends estimated from these charts compare favorably with experimental F-3 and F-4 ratings. Because of the unusual behavior of some of the aromatic blends in the F-3 engine, the charts for aromatic-paraffinic blends are probably less accurate than the charts for purely paraffinic blends.

Stereoselective preparation of quaternary 2-vinyl sphingosines and ceramides and their effect on basal sphingolipid metabolism.

PubMed

Calderón, Raquel; Mercadal, Nerea; Abad, José Luis; Ariza, Xavier; Delgado, Antonio; Garcia, Jordi; Rodríguez, Aleix; Fabriàs, Gemma

2017-06-01

The dicyclohexylborane-mediated addition of allene 1 to (E)-2-tridecenal affords a quaternary protected 2-amino-2-vinyl-1,3-diol in good yield as a single diastereomer. This compound is readily transformed into the four stereoisomers of the quaternary (E)-2-vinyl analogs of sphingosine. The metabolic fate and the effect of these compounds on the basal sphingolipid metabolism in human A549 lung adenocarcinoma cells has been studied, together with the ceramide analog of the most relevant vinylsphingosine derivative. Copyright © 2017 Elsevier B.V. All rights reserved.

Using Generic and Pesticide DRASTIC GIS-based models for vulnerability assessment of the Quaternary aquifer at Sohag, Egypt

NASA Astrophysics Data System (ADS)

Ahmed, Ayman A.

2009-07-01

Groundwater resources in the Sohag area, Egypt are currently threatened by contamination from municipal and industrial activities, and agricultural pesticides. To cope with the growing population, there has been development in the desert zone on both sides of the Nile Valley including agricultural investment areas, wastewater disposal sites, new urban areas, and industry. Use of agrochemicals in the old cultivated and newly reclaimed lands and wastewater disposal sites in the study area represent the most hazardous contamination sources. Prevention of contamination and management of the Quaternary aquifer is urgently needed. To address vulnerability assessment of the Quaternary aquifer, the Generic and Pesticide DRASTIC GIS-based models have been used. The Generic DRASTIC index ranged between 94 and 189, and the Pesticide DRASTIC index ranged between 94 and 226. The results showed that 83% of the Quaternary aquifer is characterized by the high and very high vulnerability classes to municipal, industrial and agricultural pesticides contamination. It was found that nearly all the development projects are located in the very high vulnerability class areas. Management alternatives for the Quaternary aquifer may be improved by application of these models, allowing sensitive groundwater sources to be protected for continuing use in the future.

Water quality of the Quaternary and Ada-Vamoosa aquifers on the Osage Reservation, Osage County, Oklahoma, 1997

USGS Publications Warehouse

Abbott, Marvin M.

2000-01-01

The project was to provide information on the quality of ground water from rural-domestic-water wells within the Osage Reservation and compare the water-quality to proximity to oil wells. About 38,500 oil wells have been drilled in the Reservation since drilling began in 1896. About 1,480 square miles or 64 percent of the Reservation is within a quarter mile of an oil well. The unconfined Quaternary sand aquifer covers about 315 square miles or about 14 percent of the Reservation and the confined Ada-Vamoosa sandstone aquifer covers about 800 square miles or about 35 percent of the Reservation. Fifty-eight percent of the Quaternary aquifer and 69 percent of the outcrop area of the Ada-Vamoosa aquifer are within a quarter mile of an oil well . One hundred twenty domestic ground-water wells were sampled from the Quaternary and Ada-Vamoosa aquifers. Forty-nine percent of the Reservation is underlain by the aquifers. Ground-water quality is good on most of the Reservation, but the use of domestic water-supply wells tend to minimize water-quality problems. Existing water-supply wells commonly are located in areas that produce usable volumes of potable water. Several constituents in samples from the Ada-Vamoosa-aquifer within a quarter mile of an oil well were significantly greater than from the aquifer not near oil wells. The constituents include specific conductance, dissolved solids, sodium, sulfate, chloride, bromide, and silica. These ions are probably derived from brine water. In the Ada-Vamoosa aquifer subgroups, 57 percent of the samples near oil wells and 24 percent of the samples not near oil wells had dissolved-solids concentrations greater than 500 milligrams per liter. The water quality in the Quaternary and Ada-Vamoosa aquifers is similar in areas where no oil wells have been drilled but is significantly different for several constituents. Median concentrations of major constituents from the Ada-Vamoosa aquifer not near oil wells were less than or equal to values from the Quaternary aquifer. Sixty-four percent of the water-quality samples from the Quaternary and 51 percent from the Ada-Vamoosa aquifers have dissolved-solids concentrations less than the secondary drinking water regulations of 500 milligrams per liter. Fifty-nine percent of the aquifer samples in the Quaternary aquifer subgroups not near oil wells and 70 percent of the samples near oil wells had dissolved solids less than 500 milligrams per liter. Areas in the Ada-Vamoosa aquifer near Hominy, Pershing, and Hula Lake have dissolved-solids concentrations greater than the secondary drinking water regulations. Water-quality samples from the Quaternary aquifer in these areas also have dissolved-solids concentrations greater than 500 milligrams per liter.

40 CFR 721.655 - Ethoxylated alkyl quaternary ammonium compound.

Code of Federal Regulations, 2010 CFR

2010-07-01

...) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.655 Ethoxylated alkyl quaternary ammonium compound. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically...

Ternary and Quaternary Composition Diagrams: An Overview of the Subject.

ERIC Educational Resources Information Center

MacCarthy, Patrick

1983-01-01

Reviews graphical methods for representing ternary and quaternary systems, focusing on use of triangular composition diagrams. Examines some of the relevant geometry of triangles in general, showing that right isosceles triangles possess some very advantageous features for representing ternary systems. (JN)

Solubility limits in quaternary SnTe-based alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Siol, Sebastian; Holder, Aaron; Ortiz, Brenden R.

2017-01-01

A combined theoretical and experimental approach was used to determine the equilibrium as well as non-equilibrium solubility lines in the quaternary Sn 1-yMn yTe 1-xSe xalloy space, revealing a large area of accessible metastable phase space.

Orthopalladation of iminophosphoranes: synthesis, structure and study of stability.

PubMed

Bielsa, Raquel; Navarro, Rafael; Soler, Tatiana; Urriolabeitia, Esteban P

2008-03-07

The reaction of Pd(OAc)(2) with polyfunctional iminophosphoranes Ph(3)P=NCH(2)CO(2)Me (1a), Ph(3)P=NCH(2)C(O)NMe(2) (1b), Ph(3)P=NCH(2)CH(2)SMe (1c) and Ph(3)P=NCH(2)-2-NC(5)H(4) (1d), gives the orthopalladated dinuclear complex [Pd(mu-Cl){C(6)H(4)(PPh(2)=NCH(2)CO(2)Me-kappa-C,N)-2}](2) (2a) and the mononuclear derivatives [PdCl{C(6)H(4)(PPh(2)=NCH(2)CONMe(2)-kappa-C,N,O)-2}] (2b), [PdCl{C(6)H(4)(PPh(2)=NCH(2)CH(2)SMe-kappa-C,N,S)-2}] (2c) and [PdCl{C(6)H(4)(PPh(2)=NCH(2)-2-NC(5)H(4)-kappa-C,N,N)-2}] (2d). The reaction implies the activation of a C-H bond in a phenyl ring of the phosphonium group, this fact being worthy of note due to the strongly deactivating nature of the phosphonium unit. The palladacycle containing the metallated carbon atom is remarkably stable toward the coordination of incoming ligands, while that formed by the iminic N atom and another heteroatom (O, 2a and 2b; S, 2c; N, 2d) is less stable and the resulting complexes can be considered as hemilabile. The X-ray crystal structures of the cyclopalladated [Pd(mu-Cl){C(6)H(4)(PPh(2)=NCH(2)CO(2)Me-kappa-C,N)-2}](2) (2a), [PdCl{C(6)H(4)(PPh(2)=NCH(2)-2-NC(5)H(4)-kappa-C,N,N)-2}] (2d), [Pd{C(6)H(4)(PPh(2)=NCH(2)CONMe(2)-kappa-C,N,O)-2}(NCMe)](ClO(4)) (7b) and [Pd{C(6)H(4)(PPh(2)NCH(2)CONMe(2)-kappa-C,N,O)-2}(py)](ClO(4)) (3b), and the coordination compound cis-[Pd(Cl)(2)(Ph(3)P=NCH(2)CH(2)SMe-kappa-N,S)] (8) are also reported.

How to clean the dirtiest place in the cell: cationic antioxidants as intramitochondrial ROS scavengers.

PubMed

Skulachev, Vladimir P

2005-01-01

Membrane-penetrating triphenyl alkyl phosphonium cations have been suggested for many years in our group as having the ability to measure mitochondrial potential were recently used by Murphy as vehicles to specifically target CoQ to mitochondria. As was shown in our group, the phosphonium derivative of CoQ (MitoQ) easily penetrates a planar bilayer phospholipid membrane as a cation, generating 60 mV electric potential (Deltapsi) per a 10-fold MitoQ gradient. This means that MitoQ should be unequally distributed across the inner mitochondrial membrane, the intramitochondrial [MitoQ] = extramitochondrial [MitoQ] x 10(3) at 180 mV Deltapsi. In line with such a calculation, Murphy and his colleagues reported that antioxidant efficiency of MitoQ added to mitochondria or cells appears to be very much higher than of CoQ. It was found that H2O2-induced apoptosis (Murphy) and the H2O2-mediated bystander killing of the cultivated cells (our group) are completely arrested by pretreatement of the cells with 10(-10) - 10(-8) M MitoQ. These effects indicate that MitoQ and similar compounds may be promising in treatment of heart attack, stroke and other diseases accompanied by massive apoptosis in the injured tissue. The very fact that: (i) MitoQ is not only accumulated by mitochondria but also can be regenerated in its reduced form by mitochondrial respiratory chain, (ii) it is the mitochondrial interior that produces a large portion of reactive oxygen species (ROS) in our body, and (iii) the most sensitive ROS targets are localized in the mitochondrial matrix suggest the MitoQ-like compounds are promising tools of molecular therapy of aerobic cells. In line with this suggestion, we found that addition of MitoQ strongly improves structural and biochemical parameters of cultivated cells. As to cationic tetrapeptides, recently advertised as mitochondrially-targeted Deltapsi-independent antioxidants, their effect is most probably mediated by an opioid activity inherent in some of these substances.

Pleistocene land bridges act as semipermeable agents of avian gene flow in Wallacea.

PubMed

Garg, Kritika M; Chattopadhyay, Balaji; Wilton, Peter R; Malia Prawiradilaga, Dewi; Rheindt, Frank E

2018-08-01

Cyclical periods of global cooling have been important drivers of biotic differentiation throughout the Quaternary. Ice age-induced sea level fluctuations can lead to changing patterns of land connections, both facilitating and disrupting gene flow. In this study, we test if species with differing life histories are differentially affected by Quaternary land connections. We used genome-wide SNPs in combination with mitochondrial gene sequences to analyse levels of divergence and gene flow between two songbird complexes across two Wallacean islands that have been repeatedly connected during glaciations. Although the two bird complexes are similar in ecological attributes, the forest and edge-inhabiting golden whistler Pachycephala pectoralis is comparatively flexible in its diet and niche requirements as compared to the henna-tailed jungle-flycatcher Cyornis colonus, which is largely restricted to the forest interior. Using population-genomic and coalescent approaches, we estimated levels of gene flow, population differentiation and divergence time between the two island populations. We observed higher levels of differentiation, an approximately two to four times deeper divergence time and near-zero levels of gene flow between the two island populations of the more forest-dependent henna-tailed jungle-flycatcher as compared to the more generalist golden whistler. Our results suggest that Quaternary land bridges act as semipermeable agents of gene flow in Wallacea, allowing only certain taxa to connect between islands while others remain isolated. Quaternary land bridges do not accommodate all terrestrial species equally, differing in suitability according to life history and species biology. More generalist species are likely to use Quaternary land connections as a conduit for gene flow between islands whereas island populations of more specialist species may continue to be reproductively isolated even during periods of Quaternary land bridges. Copyright © 2018 Elsevier Inc. All rights reserved.

Paleontology to policy: the Quaternary history of Southeast Asian tapirs (Tapiridae) in relation to large mammal species turnover, with a proposal for conservation of Malayan tapir by reintroduction to Borneo.

PubMed

Cranbrook, Earl Of; Piper, Philip J

2013-03-01

The Southeast Asian zoogeographical region is divided into Indochinese, Sundaic and Philippine subregions. Two clades of tapirs, Tapirus spp., have been recognized in Quaternary Southeast Asia. A review of sites at which they occurred shows that representatives of both clades, one of which was the ancestral Malayan tapir Tapirus indicus, co-existed with a diversity of other Pleistocene mammal megafauna. The process of replacement of archaic large mammals was progressive and prolonged through the Quaternary. Zooarcheological investigation has extended knowledge of the former occurrence and distribution of tapirs and other large mammals of the region, with discoveries beyond the outer limits of their previously known ranges. These large mammals were subjected to paleoenvironmental changes as a consequence of the Quaternary cycles of glacial and interglacial periods. Archeological evidence suggests that hunting pressure has intensified the effects of altered environments, leading ultimately to the local disappearance of the Malayan tapir in most of Southeast Asia, including Borneo. The survival of the Malayan tapir through the Quaternary until the present shows that the species is both resilient to environmental change and flexible in its ecological re'uirements and, given proper protection, could continue to inhabit tropical Southeast Asia. To assist the species conservation, reintroduction is proposed from the remaining range of Malayan tapir in the wild, to suitable sites of past occurrence in Borneo, where these ancient survivors of the Quaternary megafauna can be accommodated and safeguarded alongside other forms of land usage. © 2012 Wiley Publishing Asia Pty Ltd, ISZS and IOZ/CAS.

3D seismic evidence of buried iceberg ploughmarks from the mid-Norwegian continental margin reveals largely persistent North Atlantic Current through the Quaternary.

PubMed

Montelli, A; Dowdeswell, J A; Ottesen, D; Johansen, S E

2018-05-01

Over 7500 buried linear and curvilinear depressions interpreted as iceberg ploughmarks were identified within the Quaternary Naust Formation from an extensive three-dimensional seismic dataset that covers ~ 40,000 km 2 of the mid-Norwegian continental margin. The morphology and net orientation of ploughmarks were mapped and analysed. These features are up to 28 km long, 700 m wide and are incised up to 31 m deep. On average, ploughmarks are incised 5 m deep, with median width of 185 m and median lengths ranging from 1.2 to 2.7 km for individual palaeo-surfaces. Width to depth ratio ranges from 8:1 to 400:1 and is on average 36:1. The presence of ploughmarks buried deeply within some palaeo-slope surfaces implies the occasional presence of very large icebergs since the middle Quaternary, suggesting that thick ice-sheet margins with fast-flowing ice streams were present in order to calve icebergs of such dimensions into the Norwegian Sea. The wide geographical distribution of ploughmarks suggests unrestricted iceberg drift and an open Norwegian Sea during the periods of iceberg calving since the early Quaternary. Ploughmark trajectory analysis demonstrates that the ocean current circulation, now dominated by the northeasterly flowing Norwegian Atlantic Current (NwAC), has largely persisted throughout the Quaternary. Despite the overall strikingly consistent pattern of iceberg drift, ploughmark mapping also shows evidence for short-lived NwAC reductions possibly related to major phases of iceberg discharge and/or meltwater pulses from the Fennoscandian Ice Sheet during the middle and late Quaternary.

Ion-pair hollow-fiber liquid-phase microextraction of the quaternary ammonium surfactant dicocodimethylammonium chloride.

PubMed

Hultgren, Sofie; Larsson, Niklas; Nilsson, Bo F; Jönsson, Jan Ake

2009-02-01

A two-phase hollow-fiber (HF) liquid-phase microextraction (LPME) method was developed for determination of a quaternary ammonium compound surfactant, dicocodimethylammonium chloride, in aqueous samples. The porous HF was fixed on a metal rod support and was impregnated with approximately 6.6 microL of organic extractant, which was immobilized in the HF pores. Surfactant extraction was facilitated by addition of carboxylic acid to the sample forming neutral ion pairs with the quaternary ammonium compound. After extraction, the analyte was transferred from the organic extractant in the fiber pores by dissolving the 1-octanol into 100 microL methanol. The methanol extract was analyzed by liquid chromatography-mass spectrometry. The method was optimized (with optimized parameters in brackets) with regard to type of organic extractant (1-octanol), fiber length (2 cm), choice and concentration of anionic carrier (600 microg L(-1) octanoate), procedure of transfer to methanol (15-min sonication), sample volume (250 mL), extraction time (17 h), pH (10), and ionic strength (50 mM carbonate). Aspects influencing repeatability in LPME of (quaternary ammonium) surfactants are discussed. The enrichment factor achieved in 250-mL carbonate buffer was around 400. Due to matrix effects, the enrichment factors achieved when industrial process water was analyzed were 120 or about 30% of that in carbonate buffer. Detection limits of 0.3 microg L(-1) in carbonate buffer and 0.9 microg L(-1) in industrial process water were obtained. If the studied compound is seen as a model substance representing quaternary dialkylated dimethylated ammonium surfactants in general, the developed method may be applied to other quaternary ammonium surfactants.

Evaluating the Significance of Paleophylogeographic Species Distribution Models in Reconstructing Quaternary Range-Shifts of Nearctic Chelonians

PubMed Central

Flecks, Morris; Ahmadzadeh, Faraham; Dambach, Johannes; Engler, Jan O.; Habel, Jan Christian; Hartmann, Timo; Hörnes, David; Ihlow, Flora; Schidelko, Kathrin; Stiels, Darius; Polly, P. David

2013-01-01

The climatic cycles of the Quaternary, during which global mean annual temperatures have regularly changed by 5–10°C, provide a special opportunity for studying the rate, magnitude, and effects of geographic responses to changing climates. During the Quaternary, high- and mid-latitude species were extirpated from regions that were covered by ice or otherwise became unsuitable, persisting in refugial retreats where the environment was compatible with their tolerances. In this study we combine modern geographic range data, phylogeny, Pleistocene paleoclimatic models, and isotopic records of changes in global mean annual temperature, to produce a temporally continuous model of geographic changes in potential habitat for 59 species of North American turtles over the past 320 Ka (three full glacial-interglacial cycles). These paleophylogeographic models indicate the areas where past climates were compatible with the modern ranges of the species and serve as hypotheses for how their geographic ranges would have changed in response to Quaternary climate cycles. We test these hypotheses against physiological, genetic, taxonomic and fossil evidence, and we then use them to measure the effects of Quaternary climate cycles on species distributions. Patterns of range expansion, contraction, and fragmentation in the models are strongly congruent with (i) phylogeographic differentiation; (ii) morphological variation; (iii) physiological tolerances; and (iv) intraspecific genetic variability. Modern species with significant interspecific differentiation have geographic ranges that strongly fluctuated and repeatedly fragmented throughout the Quaternary. Modern species with low genetic diversity have geographic distributions that were highly variable and at times exceedingly small in the past. Our results reveal the potential for paleophylogeographic models to (i) reconstruct past geographic range modifications, (ii) identify geographic processes that result in genetic bottlenecks; and (iii) predict threats due to anthropogenic climate change in the future. PMID:24130664

Influence of the substituents on the electronic and electrochemical properties of a new square-planar nickel-bis(quinoxaline-6,7-dithiolate) system: synthesis, spectroscopy, electrochemistry, crystallography, and theoretical investigation.

PubMed

Bolligarla, Ramababu; Reddy, Samala Nagaprasad; Durgaprasad, Gummadi; Sreenivasulu, Vudagandla; Das, Samar K

2013-01-07

We describe the synthesis, crystal structures, electronic absorption spectra, and electrochemistry of a series of square-planar nickel-bis(quinoxaline-6,7-dithiolate) complexes with the general formula [Bu(4)N](2)[Ni(X(2)6,7-qdt)(2)], where X = H (1a), Ph (2a), Cl (3), and Me (4). The solution and solid-state electronic absorption spectral behavior and electrochemical properties of these compounds are strongly dependent on the electron donating/accepting nature of the substituent X, attached to the quinoxaline-6,7-dithiolate ring in the system [Bu(4)N](2)[Ni(X(2)6,7-qdt)(2)]. Particularly, the charge transfer (CT) transition bands observed in the visible region are greatly affected by the electronic nature of the substituent. A possible explanation for this influence of the substituents on electronic absorption and electrochemistry is described based on highest occupied molecular orbital (HOMO) to lowest unoccupied molecular orbital (LUMO) gaps, which is further supported by ground-state electronic structure calculations. In addition to this, the observed CT bands in all the complexes are sensitive to the solvent polarity. Interestingly, compounds 1a, 2a, 3, and 4 undergo reversible oxidation at very low oxidation potentials appearing at E(1/2) = +0.12 V, 0.033 V, 0.18 V, and 0.044 V vs Ag/AgCl, respectively, in MeOH solutions, corresponding to the respective couples [Ni(X(2)6,7-qdt)(2)](-)/[Ni(X(2)6,7-qdt)(2)](2-). Compounds 1a, 3, and 4 have been characterized unambiguously by single crystal X-ray structural analysis; compound 2a could not be characterized by single crystal X-ray structure determination because of the poor quality of the concerned crystals. Thus, we have synthesized the tetraphenyl phosphonium salt of the complex anion of 2a, [PPh(4)](2)[Ni(Ph(2)6,7-qdt)(2)]·3DMF (2b) for its structural characterization.

Synthesis and Functional Assessment of a Novel Fatty Acid Probe, ω-Ethynyl Eicosapentaenoic Acid Analog, to Analyze the in Vivo Behavior of Eicosapentaenoic Acid.

PubMed

Tokunaga, Tomohisa; Watanabe, Bunta; Sato, Sho; Kawamoto, Jun; Kurihara, Tatsuo

2017-08-16

Eicosapentaenoic acid (EPA) is an ω-3 polyunsaturated fatty acid that plays various beneficial roles in organisms from bacteria to humans. Although its beneficial physiological functions are well-recognized, a molecular probe that enables the monitoring of its in vivo behavior without abolishing its native functions has not yet been developed. Here, we designed and synthesized an ω-ethynyl EPA analog (eEPA) as a tool for analyzing the in vivo behavior and function of EPA. eEPA has an ω-ethynyl group tag in place of the ω-methyl group of EPA. An ethynyl group has a characteristic Raman signal and can be visualized by Raman scattering microscopy. Moreover, this group can specifically react in situ with azide compounds, such as those with fluorescent group, via click chemistry. In this study, we first synthesized eEPA efficiently based on the following well-known strategies. To introduce four C-C double bonds, a coupling reaction between terminal acetylene and propargylic halide or tosylate was employed, and then, by simultaneous and stereoselective partial hydrogenation with P-2 nickel, the triple bonds were converted to cis double bonds. One double bond and an ω-terminal C-C triple bond were introduced by Wittig reaction with a phosphonium salt harboring an ethynyl group. Then, we evaluated the in vivo function of the resulting probe by using an EPA-producing bacterium, Shewanella livingstonensis Ac10. This cold-adapted bacterium inducibly produces EPA at low temperatures, and the EPA-deficient mutant (ΔEPA) shows growth retardation and abnormal morphology at low temperatures. When eEPA was exogenously supplemented to ΔEPA, eEPA was incorporated into the membrane phospholipids as an acyl chain, and the amount of eEPA was about 5% of the total fatty acids in the membrane, which is comparable to the amount of EPA in the membrane of the parent strain. Notably, by supplementation with eEPA, the growth retardation and abnormal morphology of ΔEPA were almost completely suppressed. These results indicated that eEPA mimics EPA well and is useful for analyzing the in vivo behavior of EPA.

Preconcentration of DNA using magnetic ionic liquids that are compatible with real-time PCR for rapid nucleic acid quantification.

PubMed

Emaus, Miranda N; Clark, Kevin D; Hinners, Paige; Anderson, Jared L

2018-04-28

Nucleic acid extraction and purification represents a major bottleneck in DNA analysis. Traditional methods for DNA purification often require reagents that may inhibit quantitative polymerase chain reaction (qPCR) if not sufficiently removed from the sample. Approaches that employ magnetic beads may exhibit lower extraction efficiencies due to sedimentation and aggregation. In this study, four hydrophobic magnetic ionic liquids (MILs) were investigated as DNA extraction solvents with the goal of improving DNA enrichment factors and compatibility with downstream bioanalytical techniques. By designing custom qPCR buffers, we directly incorporated DNA-enriched MILs including trihexyl(tetradecyl)phosphonium tris(hexafluoroacetylaceto)nickelate(II) ([P 6,6,6,14 + ][Ni(hfacac) 3 - ]), [P 6,6,6,14 + ] tris(hexafluoroacetylaceto)colbaltate(II) ([Co(hfacac) 3 - ]), [P 6,6,6,14 + ] tris(hexafluoroacetylaceto)manganate(II) ([Mn(hfacac) 3 - ]), or [P 6,6,6,14 + ] tetrakis(hexafluoroacetylaceto)dysprosate(III) ([Dy(hfacac) 4 - ]) into reaction systems, thereby circumventing the need for time-consuming DNA recovery steps. Incorporating MILs into the reaction buffer did not significantly impact the amplification efficiency of the reaction (91.1%). High enrichment factors were achieved using the [P 6,6,6,14 + ][Ni(hfacac) 3 - ] MIL for the extraction of single-stranded and double-stranded DNA with extraction times as short as 2 min. When compared to a commercial magnetic bead-based platform, the [P 6,6,6,14 + ][Ni(hfacac) 3 - ] MIL was capable of producing higher enrichment factors for single-stranded DNA and similar enrichment factors for double-stranded DNA. The MIL-based method was applied for the extraction and direct qPCR amplification of mutation prone-KRAS oncogene fragment in plasma samples. Graphical abstract Magnetic ionic liquid solvents are shown to preconcentrate sufficient KRAS DNA template from an aqueous solution in as short as 2 min without using chaotropic salts or toxic organic solvents. By using custom-designed qPCR buffers, DNA can be directly amplified and quantified from four MILs examined in this study.