A "by-productless" cellulose foaming agent for use in imidazolium ionic liquids.

PubMed

Scott, Janet L; Unali, Gianfranco; Perosa, Alvise

2011-03-14

Cellulose foams, or sponges, are produced from solutions in ionic liquids by the aqueous acid mediated decomposition of 1-alkyl-3-methylimidazolium-2-carboxylates, where the alkyl group and acid may be selected such that the by-product is the ionic liquid solvent: a by-productless foaming.

Comparison of Dilute Acid and Ionic Liquid Pretreatment of Switchgrass: Biomass Recalcitrance, Delignification and Enzymatic Saccharification

USDA-ARS?s Scientific Manuscript database

The efficiency of two biomass pretreatment technologies, dilute acid hydrolysis and dissolution in an ionic liquid, are compared in terms of delignification, saccharification efficiency and saccharide yields with switchgrass serving as a model bioenergy crop. When subject to ionic liquid pretreatme...

Ionic-Liquid-Mediated Extraction and Separation Processes for Bioactive Compounds: Past, Present, and Future Trends.

PubMed

Ventura, Sónia P M; E Silva, Francisca A; Quental, Maria V; Mondal, Dibyendu; Freire, Mara G; Coutinho, João A P

2017-05-24

Ionic liquids (ILs) have been proposed as promising media for the extraction and separation of bioactive compounds from the most diverse origins. This critical review offers a compilation on the main results achieved by the use of ionic-liquid-based processes in the extraction and separation/purification of a large range of bioactive compounds (including small organic extractable compounds from biomass, lipids, and other hydrophobic compounds, proteins, amino acids, nucleic acids, and pharmaceuticals). ILs have been studied as solvents, cosolvents, cosurfactants, electrolytes, and adjuvants, as well as used in the creation of IL-supported materials for separation purposes. The IL-based processes hitherto reported, such as IL-based solid-liquid extractions, IL-based liquid-liquid extractions, IL-modified materials, and IL-based crystallization approaches, are here reviewed and compared in terms of extraction and separation performance. The key accomplishments and future challenges to the field are discussed, with particular emphasis on the major lacunas found within the IL community dedicated to separation processes and by suggesting some steps to overcome the current limitations.

Ionic-Liquid-Mediated Extraction and Separation Processes for Bioactive Compounds: Past, Present, and Future Trends

PubMed Central

2017-01-01

Ionic liquids (ILs) have been proposed as promising media for the extraction and separation of bioactive compounds from the most diverse origins. This critical review offers a compilation on the main results achieved by the use of ionic-liquid-based processes in the extraction and separation/purification of a large range of bioactive compounds (including small organic extractable compounds from biomass, lipids, and other hydrophobic compounds, proteins, amino acids, nucleic acids, and pharmaceuticals). ILs have been studied as solvents, cosolvents, cosurfactants, electrolytes, and adjuvants, as well as used in the creation of IL-supported materials for separation purposes. The IL-based processes hitherto reported, such as IL-based solid–liquid extractions, IL-based liquid–liquid extractions, IL-modified materials, and IL-based crystallization approaches, are here reviewed and compared in terms of extraction and separation performance. The key accomplishments and future challenges to the field are discussed, with particular emphasis on the major lacunas found within the IL community dedicated to separation processes and by suggesting some steps to overcome the current limitations. PMID:28151648

Metal-chelating active packaging film enhances lysozyme inhibition of Listeria monocytogenes.

PubMed

Roman, Maxine J; Decker, Eric A; Goddard, Julie M

2014-07-01

Several studies have demonstrated that metal chelators enhance the antimicrobial activity of lysozyme. This study examined the effect of metal-chelating active packaging film on the antimicrobial activity of lysozyme against Listeria monocytogenes. Polypropylene films were surface modified by photoinitiated graft polymerization of acrylic acid (PP-g-PAA) from the food contact surface of the films to impart chelating activity based on electrostatic interactions. PP-g-PAA exhibited a carboxylic acid density of 113 ± 5.4 nmol cm(-2) and an iron chelating activity of 53.7 ± 9.8 nmol cm(-2). The antimicrobial interaction of lysozyme and PP-g-PAA depended on growth media composition. PP-g-PAA hindered lysozyme activity at low ionic strength (2.48-log increase at 64.4 mM total ionic strength) and enhanced lysozyme activity at moderate ionic strength (5.22-log reduction at 120 mM total ionic strength). These data support the hypothesis that at neutral pH, synergy between carboxylate metal-chelating films (pKa(bulk) 6.45) and lysozyme (pI 11.35) is optimal in solutions of moderate to high ionic strength to minimize undesirable charge interactions, such as lysozyme absorption onto film. These findings suggest that active packaging, which chelates metal ions based on ligand-specific interactions, in contrast to electrostatic interactions, may improve antimicrobial synergy. This work demonstrates the potential application of metal-chelating active packaging films to enhance the antimicrobial activity of membrane-disrupting antimicrobials, such as lysozyme.

Why is hydrofluoric acid a weak acid?

PubMed

Ayotte, Patrick; Hébert, Martin; Marchand, Patrick

2005-11-08

The infrared vibrational spectra of amorphous solid water thin films doped with HF at 40 K reveal a strong continuous absorbance in the 1000-3275 cm(-1) range. This so-called Zundel continuum is the spectroscopic hallmark for aqueous protons. The extensive ionic dissociation of HF at such low temperature suggests that the reaction enthalpy remains negative down to 40 K. These observations support the interpretation that dilute HF aqueous solutions behave as weak acids largely due to the large positive reaction entropy resulting from the structure making character of the hydrated fluoride ion.

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.

Tuning transport selectivity of ionic species by phosphoric acid gradient in positively charged nanochannel membranes.

PubMed

Yang, Meng; Yang, Xiaohai; Wang, Kemin; Wang, Qing; Fan, Xin; Liu, Wei; Liu, Xizhen; Liu, Jianbo; Huang, Jin

2015-02-03

The transport of ionic species through a nanochannel plays important roles in fundamental research and practical applications of the nanofluidic device. Here, we demonstrated that ionic transport selectivity of a positively charged nanochannel membrane can be tuned under a phosphoric acid gradient. When phosphoric acid solution and analyte solution were connected by the positively charged nanochannel membrane, the faster-moving analyte through the positively charged nanochannel membrane was the positively charged dye (methylviologen, MV(2+)) instead of the negatively charged dye (1,5-naphthalene disulfonate, NDS(2-)). In other words, a reversed ion selectivity of the nanochannel membranes can be found. It can be explained as a result of the combination of diffusion, induced electroosmosis, and induced electrophoresis. In addition, the influencing factors of transport selectivity, including concentration of phosphoric acid, penetration time, and volume of feed solution, were also investigated. The results showed that the transport selectivity can further be tuned by adjusting these factors. As a method of tuning ionic transport selectivity by establishing phosphoric acid gradient, it will be conducive to improving the separation of ionic species.

Nanopore analysis of polymers in solution.

NASA Astrophysics Data System (ADS)

Deamer, David

2002-03-01

Nanopores represent a novel approach for investigating macromolecules in solution. Polymers that have been analyzed by this technique include polyethylene glycol (PEG), certain proteins and nucleic acids. The a-hemolysin pore inserted into lipid bilayers provides continuous non-gated ion current through a pore diameter of approximately 1.5 - 2 nm. Nucleic acid molecules can be driven through the pore by imposing a voltage across the supporting membrane. Single stranded, but not double stranded nucleic acids pass through in strict linear sequence from one end of the molecule to the other. While in the pore, the molecule reduces ionic current, and properties of the ionic current blockade such as duration, mean amplitude and modulations of amplitude provide information about structure and composition of the nucleic acid. For a given molecular species, the duration of the blockade is a function of chain length, and the rate of blockades is linearly related to concentration. More recent studies have shown that the a-hemolysin nanopore can discriminate between synthetic DNA molecules differing by a single base pair or even a single nucleotide. These results indicate that a nanopore may have the resolution required for nucleic acid sequencing applications.

Ionic supramolecular networks fully based on chemicals coming from renewable sources.

PubMed

Aboudzadeh, Ali; Fernandez, Mercedes; Muñoz, Maria Eugenia; Santamaría, Antxon; Mecerreyes, David

2014-02-01

New supramolecular ionic networks are synthesized by proton transfer reaction between a bio-based fatty diamine molecule (Priamine 1074) and a series of naturally occurring carboxylic acids such as malonic acid, citric acid, tartaric acid, and 2,5-furandicarboxylic acid. The resulting solid soft material exhibits a thermoreversible transition becoming a viscoelastic liquid at high temperatures. All the networks show an elastic behavior at low temperatures/high frequencies, with elastic modulus values ranging from 4.5 × 10(6) to 4.5 × 10(7) Pa and soft network to liquid transitions T(nl) between -10 and 60 °C. The supramolecular ionic network based on cationic Priamine 1074 and anionic citrate shows promising self-healing properties at room temperature as well as relatively high ionic conductivity values close to 10(-6) S cm(-1). © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Amino acid ionic liquids.

PubMed

Ohno, Hiroyuki; Fukumoto, Kenta

2007-11-01

The preparation of ionic liquids derived from amino acids, and their properties, are outlined. Since amino acids have both a carboxylic acid residue and an amino group in a single molecule, they can be used as either anions or cations. These groups are also useful in their ability to introduce functional group(s). Twenty different natural amino acids were used as anions, to couple with the 1-ethyl-3-methylimidazolium cation. The salts obtained were all liquid at room temperature. The properties of the resulting ionic liquids (AAILs) depend on the side groups of the amino acids involved. These AAILs, composed of an amino acid with some functional groups such as a hydrogen bonding group, a charged group, or an aromatic ring, had an increased glass transition (or melting) temperature and/or higher viscosity as a result of additional interactions among the ions. Viscosity is reduced and the decomposition temperature of imidazolium-type salts is improved by using the tetrabutylphosphonium cation. The chirality of AAILs was maintained even upon heating to 150 degrees C after acetylation of the free amino group. The amino group was also modified to introduce a strong acid group so as to form hydrophobic and chiral ionic liquids. Unique phase behavior of the resulting hydrophobic ionic liquids and water mixture is found; the mixture is clearly phase separated at room temperature, but the solubility of water in this IL increases upon cooling, to give a homogeneous solution. This phase change is reversible, and separation occurs again by raising the temperature a few degrees. It is extraordinary for an IL/water mixture to display such behavior with a lower critical solution temperature. Some likely applications are proposed for these amino acid derived ionic liquids.

Evidence for an Ionic Intermediate in the Transformation of Fatty Acid Hydroperoxide by a Catalase-related Allene Oxide Synthase from the Cyanobacterium Acaryochloris marina*

PubMed Central

Gao, Benlian; Boeglin, William E.; Zheng, Yuxiang; Schneider, Claus; Brash, Alan R.

2009-01-01

Allene oxides are reactive epoxides biosynthesized from fatty acid hydroperoxides by specialized cytochrome P450s or by catalase-related hemoproteins. Here we cloned, expressed, and characterized a gene encoding a lipoxygenase-catalase/peroxidase fusion protein from Acaryochloris marina. We identified novel allene oxide synthase (AOS) activity and a by-product that provides evidence of the reaction mechanism. The fatty acids 18.4ω3 and 18.3ω3 are oxygenated to the 12R-hydroperoxide by the lipoxygenase domain and converted to the corresponding 12R,13-epoxy allene oxide by the catalase-related domain. Linoleic acid is oxygenated to its 9R-hydroperoxide and then, surprisingly, converted ∼70% to an epoxyalcohol identified spectroscopically and by chemical synthesis as 9R,10S-epoxy-13S-hydroxyoctadeca-11E-enoic acid and only ∼30% to the 9R,10-epoxy allene oxide. Experiments using oxygen-18-labeled 9R-hydroperoxide substrate and enzyme incubations conducted in H218O indicated that ∼72% of the oxygen in the epoxyalcohol 13S-hydroxyl arises from water, a finding that points to an ionic intermediate (epoxy allylic carbocation) during catalysis. AOS and epoxyalcohol synthase activities are mechanistically related, with a reacting intermediate undergoing a net hydrogen abstraction or hydroxylation, respectively. The existence of epoxy allylic carbocations in fatty acid transformations is widely implicated although for AOS reactions, without direct experimental support. Our findings place together in strong association the reactions of allene oxide synthesis and an ionic reaction intermediate in the AOS-catalyzed transformation. PMID:19531485

Atomic Force Microscopy and MD Simulations Reveal Pore-Like Structures of All-D-Enantiomer of Alzheimer’s β-Amyloid Peptide: Relevance to the Ion Channel Mechanism of AD Pathology

PubMed Central

Connelly, Laura; Arce, Fernando Teran; Jang, Hyunbum; Capone, Ricardo; Kotler, Samuel A.; Ramachandran, Srinivasan; Kagan, Bruce L.; Nussinov, Ruth; Lal, Ratnesh

2012-01-01

Alzheimer’s disease (AD) is a protein misfolding disease characterized by a build-up of β-amyloid (Aβ) peptide as senile plaques, uncontrolled neurodegeneration, and memory loss. AD pathology is linked to the destabilization of cellular ionic homeostasis and involves Aβ peptide-plasma membrane interactions. In principle, there are two possible ways through which disturbance of the ionic homeostasis can take place: directly, where the Aβ peptide either inserts into the membrane and creates ion-conductive pores or destabilizes the membrane organization; or, indirectly, where the Aβ peptide interacts with existing cell membrane receptors. To distinguish between these two possible types of Aβ-membrane interactions, we took advantage of the biochemical tenet that ligand-receptor interactions are stereospecific; L-amino acid peptides, but not their D-counterparts, bind to cell membrane receptors. However, with respect to the ion channel-mediated mechanism, like L-amino acids, D-amino acid peptides will also form ion channel-like structures. Using atomic force microscopy (AFM) we imaged the structures of both D- and L-enantiomers of the full length Aβ1-42 when reconstituted in lipid bilayers. AFM imaging shows that both L- and D-Aβ isomers form similar channel-like structures. Molecular dynamics (MD) simulations support the AFM imaged 3D structures. Earlier we have shown that D-Aβ1-42 channels conduct ions similarly to their L-counter parts. Taken together, our results support the direct mechanism of Aβ ion channel-mediated destabilization of ionic homeostasis rather than the indirect mechanism through Aβ interaction with membrane receptors. PMID:22217000

Synergistic Interaction within Bifunctional Ruthenium Nanoparticle/SILP Catalysts for the Selective Hydrodeoxygenation of Phenols.

PubMed

Luska, Kylie L; Migowski, Pedro; El Sayed, Sami; Leitner, Walter

2015-12-21

Ruthenium nanoparticles immobilized on acid-functionalized supported ionic liquid phases (Ru NPs@SILPs) act as efficient bifunctional catalysts in the hydrodeoxygenation of phenolic substrates under batch and continuous flow conditions. A synergistic interaction between the metal sites and acid groups within the bifunctional catalyst leads to enhanced catalytic activities for the overall transformation as compared to the individual steps catalyzed by the separate catalytic functionalities. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structure of the Stern layer in Phospholipid Systems

NASA Astrophysics Data System (ADS)

Vangaveti, Sweta; Travesset, Alex

2011-03-01

The structure of the Stern layer in Phospholipid Systems results from a subtle competition of salt concentration, ionic valence, specific ionic-phospolipid interactions and pH. It becomes very challenging to develop a rigorous theory that encompasses all these effects, yet its understanding is extremely relevant for both model and biological systems, as the structure of the Stern layer determines the interactions of phospholipids with proteins or electrostatic phase separation (rafts). In this talk we will present our theoretical model for the Stern Layer and discuss how all these effects are included. Particularly emphasis is made to Phosphoinositides and Phosphatidic acid. This work is supported by grant NSF DMR-0748475.

Natural terpene derivatives as new structural task-specific ionic liquids to enhance the enantiorecognition of acidic enantiomers on teicoplanin-based stationary phase by high-performance liquid chromatography.

PubMed

Flieger, Jolanta; Feder-Kubis, Joanna; Tatarczak-Michalewska, Małgorzata; Płazińska, Anita; Madejska, Anna; Swatko-Ossor, Marta

2017-06-01

We present the specific cooperative effect of a semisynthetic glycopeptide antibiotic teicoplanin and chiral ionic liquids containing the (1R,2S,5R)-(-)-menthol moiety on the chiral recognition of enantiomers of mandelic acid, vanilmandelic acid, and phenyllactic acid. Experiments were performed chromatographically on an Astec Chirobiotic T chiral stationary phase applying the mobile phase with the addition of the chiral ionic liquids. The stereoselective binding of enantiomers to teicoplanin in presence of new chiral ionic liquids were evaluated applying thermodynamic measurements and the docking simulations. Both the experimental and theoretical methods revealed that the chiral recognition of enantiomers in the presence of new chiral ionic liquids was enthalpy driven. The changes of the teicoplanin conformation occurring upon binding of the chiral ionic liquids are responsible for the differences in the standard changes in Gibbs energy (ΔG 0 ) values obtained for complexes formed by the R and S enantiomers and teicoplanin. Docking simulations revealed the steric adjustment between the chiral ionic liquids cyclohexane ring (chair conformation) and the β-d-glucosamine ring of teicoplanin and additionally hydrophobic interactions between the decanoic aliphatic chain of teicoplanin and the alkyl group of the tested salts. The obtained terpene derivatives can be considered as "structural task-specific ionic liquids" responsible for enhancing the chiral resolution in synergistic systems with two chiral selectors. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Vaporization of protic ionic liquids derived from organic superbases and short carboxylic acids.

PubMed

Ribeiro, Filipe M S; Lima, Carlos F R A C; Vaz, Inês C M; Rodrigues, Ana S M C; Sapei, Erlin; Melo, André; Silva, Artur M S; Santos, Luís M N B F

2017-06-28

This work presents a comprehensive evaluation of the phase behaviour and cohesive enthalpy of protic ionic liquids (PILs) composed of 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) organic superbases with short-chain length (acetic, propionic and butyric) carboxylic acids. Glass transition temperatures, T g , and enthalpies of vaporization, ΔH vap , were measured for six [BH][A] (1 : 1) PILs (B = DBN, DBU; A = MeCOO, EtCOO, nPrCOO), revealing more significant changes upon increasing the number of -CH 2 - groups in the base than in the acid. The magnitude of ΔH vap evidences that liquid PILs have a high proportion of ions, although the results also indicate that in DBN PILs the concentration of neutral species is not negligible. In the gas phase, these PILs exist as a distribution of ion pairs and isolated neutral species, with speciation being dependent on the temperature and pressure conditions - at high temperatures and low pressures the separated neutral species dominate. The higher T g and ΔH vap of the DBU PILs are explained by the stronger basicity of DBU (as supported by NMR and computational calculations), which increases the extent of proton exchange and the ionic character of the corresponding PILs, resulting in stronger intermolecular interactions in condensed phases.

Actinide recovery process

DOEpatents

Muscatello, Anthony C.; Navratil, James D.; Saba, Mark T.

1987-07-28

Process for the removal of plutonium polymer and ionic actinides from aqueous solutions by absorption onto a solid extractant loaded on a solid inert support such as polystyrenedivinylbenzene. The absorbed actinides can then be recovered by incineration, by stripping with organic solvents, or by acid digestion. Preferred solid extractants are trioctylphosphine oxide and octylphenyl-N,N-diisobutylcarbamoylmethylphosphine oxide and the like.

Actinide recovery process

DOEpatents

Muscatello, A.C.; Navratil, J.D.; Saba, M.T.

1985-06-13

Process for the removal of plutonium polymer and ionic actinides from aqueous solutions by absorption onto a solid extractant loaded on a solid inert support such as polystyrene-divinylbenzene. The absorbed actinides can then be recovered by incineration, by stripping with organic solvents, or by acid digestion. Preferred solid extractants are trioctylphosphine oxide and octylphenyl-N,N-diisobutylcarbamoylmethylphosphine oxide and the like. 2 tabs.

Evaluation of ionic liquid stationary phases for one dimensional gas chromatography-mass spectrometry and comprehensive two dimensional gas chromatographic analyses of fatty acids in marine biota.

PubMed

Gu, Qun; David, Frank; Lynen, Frédéric; Vanormelingen, Pieter; Vyverman, Wim; Rumpel, Klaus; Xu, Guowang; Sandra, Pat

2011-05-20

Ionic liquid stationary phases were tested for one dimensional gas chromatography-mass spectrometry (GC-MS) and comprehensive two dimensional gas chromatography (GC×GC) of fatty acid methyl esters from algae. In comparison with polyethylene glycol and cyanopropyl substituted polar stationary phases, ionic liquid stationary phases SLB-IL 82 and SLB-IL 100 showed comparable resolution, but lower column bleeding with MS detection, resulting in better sensitivity. The selectivity and polarity of the ionic liquid phases are similar to a highly polar biscyanopropyl-silicone phase (e.g. HP-88). In GC×GC, using an apolar polydimethyl siloxane×polar ionic liquid column combination, an excellent group-type separation of fatty acids with different carbon numbers and number of unsaturations was obtained, providing information that is complementary to GC-MS identification. Copyright © 2011 Elsevier B.V. All rights reserved.

Microwave-Assisted Resolution of α-Lipoic Acid Catalyzed by an Ionic Liquid Co-Lyophilized Lipase.

PubMed

Liu, Ning; Wang, Lei; Wang, Zhi; Jiang, Liyan; Wu, Zhuofu; Yue, Hong; Xie, Xiaona

2015-05-29

The combination of the ionic liquid co-lyophilized lipase and microwave irradiation was used to improve enzyme performance in enantioselective esterification of α-lipoic acid. Effects of various reaction conditions on enzyme activity and enantioselectivity were investigated. Under optimal condition, the highest enantioselectivity (E = 41.2) was observed with a high enzyme activity (178.1 μmol/h/mg) when using the ionic liquid co-lyophilized lipase with microwave assistance. Furthermore, the ionic liquid co-lyophilized lipase exhibited excellent reusability under low power microwave.

Electrochemical Polishing Applications and EIS of a Novel Choline Chloride-Based Ionic Liquid

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

Wixtrom, Alex I.; Buhler, Jessica E.; Reece, Charles E.

2013-06-01

Minimal surface roughness is a critical feature for high-field superconducting radio frequency (SRF) cavities used to engineer particle accelerators. Current methods for polishing Niobium cavities typically utilize solutions containing a mixture of concentrated sulfuric and hydrofluoric acid. Polishing processes such as these are effective, yet there are many hazards and costs associated with the use (and safe disposal) of the concentrated acid solutions. An alternative method for electrochemical polishing of the cavities was explored using a novel ionic liquid solution containing choline chloride. Potentiostatic electrochemical impedance spectroscopy (EIS) was used to analyze the ionic polishing solution. Final surface roughness ofmore » the Nb was found to be comparable to that of the acid-polishing method, as assessed by atomic force microscopy (AFM). This indicates that ionic liquid-based electrochemical polishing of Nb is a viable replacement for acid-based methods for preparation of SRF cavities.« less

Ionic protein-lipid interaction at the plasma membrane: what can the charge do?

PubMed

Li, Lunyi; Shi, Xiaoshan; Guo, Xingdong; Li, Hua; Xu, Chenqi

2014-03-01

Phospholipids are the major components of cell membranes, but they have functional roles beyond forming lipid bilayers. In particular, acidic phospholipids form microdomains in the plasma membrane and can ionically interact with proteins via polybasic sequences, which can have functional consequences for the protein. The list of proteins regulated by ionic protein-lipid interaction has been quickly expanding, and now includes membrane proteins, cytoplasmic soluble proteins, and viral proteins. Here we review how acidic phospholipids in the plasma membrane regulate protein structure and function via ionic interactions, and how Ca(2+) regulates ionic protein-lipid interactions via direct and indirect mechanisms. Copyright © 2014 Elsevier Ltd. All rights reserved.

NMR Studies of Mass Transport in New Conducting Media for Fuel Cells

DTIC Science & Technology

2009-01-01

PEM films, for example those containing phosphoric acid and ionic liquids . Dynamical processes are probed at the short range by spin-lattice...structural environments of muticomponent PEM films, for example those containing phosphoric acid and ionic liquids . Dynamical processes are probed at the...correlation between water diffusivity and proton conductivity in the nanocomposites Transport properties of several ionic liquids (IL’s) and membranes

Ionic complexation as a non-covalent approach for the design of folate anchored rifampicin Gantrez nanoparticles.

PubMed

Date, Praveen V; Patel, Mitesh D; Majee, Sharmila B; Samad, Abdul; Devarajan, Padma V

2013-05-01

The present study discloses the design of folate anchored Rifampicin-Poly methylvinylether maleic anhydride copolymer (Gantrez AN-119, Gantrez) nanoparticles (RFMGzFa) by ionic complexation. Folic acid was anchored to the preformed drug loaded nanoparticles. Folic acid was anchored in different concentration by simply varying the amount of folic acid added during preparation. RFMGzFa nanoparticles were prepared by emulsion solvent diffusion method. Gantrez AN-119 rapidly hydrolyzes in aqueous medium releasing carboxylic acid groups, to create an acidic environment. This facilitates protonation and subsequent ionic complexation of folic acid with the carboxylic groups, to enable anchoring. FTIR spectra confirmed this interaction. Infrared imaging revealed distribution of folic acid across the nanoparticle surface. Nanoparticles were obtained in the size range 350-450 nm with RFM loading of 12-14% w/w. Zeta potential confirmed colloidal stability. TEM/SEM revealed spherical morphology. RFMGzFa nanoparticles exhibited sustained release of RFM and folic acid. Folic acid showed sustained release upto 12 h, which was ion exchange mediated. A 480% enhancement in RFM uptake with RFMGzFa nanoparticles compared to 300% with RFMGz nanoparticles in-vitro, in human macrophage cell line U-937, suggested the role of folic acid in folate receptor mediated uptake. Ionic complexation represents a simple non-covalent approach for anchoring folic acid on polymeric nanoparticles of Gantrez.

Channels, pumps, and exchangers in the gill and kidney of freshwater fishes: their role in ionic and acid-base regulation.

PubMed

Perry, S F; Shahsavarani, A; Georgalis, T; Bayaa, M; Furimsky, M; Thomas, S L Y

2003-11-01

In freshwater fishes, the gill and kidney are intricately involved in ionic and acid-base regulation owing to the presence of numerous ion channels, pumps, or exchangers. This review summarizes recent developments in branchial and renal ion transport physiology and presents several models that integrate epithelial ion and acid-base movements in freshwater fishes. At the gill, three cell types are potentially involved in ionic uptake: pavement cells, mitochondria-rich (MR) PNA(+) cells, and MR PNA(-) cells. The transfer of acidic or basic equivalents between the fish and its environment is accomplished largely by the gill and is appropriately regulated to correct acid-base imbalances. The kidney, while less important than the gill in overall acid or base excretion, has an essential role in regulating systemic acid-base balance by controlling HCO(3) (-) reabsorption from the filtrate. Copyright 2003 Wiley-Liss, Inc.

Brønsted acidity of protic ionic liquids: a modern ab initio valence bond theory perspective.

PubMed

Patil, Amol Baliram; Mahadeo Bhanage, Bhalchandra

2016-09-21

Room temperature ionic liquids (ILs), especially protic ionic liquids (PILs), are used in many areas of the chemical sciences. Ionicity, the extent of proton transfer, is a key parameter which determines many physicochemical properties and in turn the suitability of PILs for various applications. The spectrum of computational chemistry techniques applied to investigate ionic liquids includes classical molecular dynamics, Monte Carlo simulations, ab initio molecular dynamics, Density Functional Theory (DFT), CCSD(t) etc. At the other end of the spectrum is another computational approach: modern ab initio Valence Bond Theory (VBT). VBT differs from molecular orbital theory based methods in the expression of the molecular wave function. The molecular wave function in the valence bond ansatz is expressed as a linear combination of valence bond structures. These structures include covalent and ionic structures explicitly. Modern ab initio valence bond theory calculations of representative primary and tertiary ammonium protic ionic liquids indicate that modern ab initio valence bond theory can be employed to assess the acidity and ionicity of protic ionic liquids a priori.

A computer program for geochemical analysis of acid-rain and other low-ionic-strength, acidic waters

USGS Publications Warehouse

Johnsson, P.A.; Lord, D.G.

1987-01-01

ARCHEM, a computer program written in FORTRAN 77, is designed primarily for use in the routine geochemical interpretation of low-ionic-strength, acidic waters. On the basis of chemical analyses of the water, and either laboratory or field determinations of pH, temperature, and dissolved oxygen, the program calculates the equilibrium distribution of major inorganic aqueous species and of inorganic aluminum complexes. The concentration of the organic anion is estimated from the dissolved organic concentration. Ionic ferrous iron is calculated from the dissolved oxygen concentration. Ionic balances and comparisons of computed with measured specific conductances are performed as checks on the analytical accuracy of chemical analyses. ARCHEM may be tailored easily to fit different sampling protocols, and may be run on multiple sample analyses. (Author 's abstract)

Novel ascorbic acid based ionic liquids for the in situ synthesis of quasi-spherical and anisotropic gold nanostructures in aqueous medium.

PubMed

Dinda, Enakshi; Si, Satyabrata; Kotal, Atanu; Mandal, Tarun K

2008-01-01

A series of newly designed ascorbic acid based room temperature ionic liquids were successfully used to prepare quasi-spherical and anisotropic gold nanostructures in an aqueous medium at ambient temperature. The synthesis of these room temperature ionic liquids involves, first, the preparation of a 1-alkyl (such as methyl, ethyl, butyl, hexyl, octyl, and decyl) derivative of 3-methylimidazolium hydroxide followed by the neutralization of the derivatised product with ascorbic acid. These ionic liquids show significantly better thermal stability and their glass transition temperature (Tg) decreases with increasing alkyl chain length. The ascorbate counter anion of these ionic liquids acts as a reducing agent for HAuCl4 to produce metallic gold and the alkylated imidazolium counter cation acts as a capping/shape-directing agent. It has been found that the nature of the ionic liquids and the mole ratio of ionic liquid to HAuCl4 has a significant effect on the morphology of the formed gold nanostructures. If an equimolar mixture of ionic liquid and HAuCl4 is used, predominantly anisotropic gold nanostructures are formed and by varying the alkyl chain length attached to imidazolium cation of the ionic liquids, various particle morphologies can formed, such as quasispherical, raspberry-like, flakes or dendritic. A probable formation mechanism for such anisotropic gold nanostructures has been proposed, which is based on the results of some control experiments.

Recovery of sugars from ionic liquid biomass liquor by solvent extraction

DOEpatents

Brennan, Timothy Charles R.; Holmes, Bradley M.; Simmons, Blake A.; Blanch, Harvey W.

2015-10-13

The present invention provides for a composition comprising a solution comprising (a) an ionic liquid (IL) or ionic liquid-aqueous (ILA) phase and (b) an organic phase, wherein the solution comprises a sugar and a boronic acid. The present invention also provides for a method of removing a sugar from a solution, comprising: (a) providing a solution comprising (i) an IL or ILA phase and (ii) an organic phase, wherein the solution comprises an IL, a sugar and a boronic acid; (b) contacting the sugar with the boronic acid to form a sugar-boronic acid complex, (c) separating the organic phase and the aqueous phase, wherein the organic phase contains the sugar-boronic acid complex, and optionally (d) separating the sugar from the organic phase.

Efficient production of free fatty acids from ionic liquid-based acid- or enzyme-catalyzed bamboo hydrolysate.

PubMed

Mi, Le; Qin, Dandan; Cheng, Jie; Wang, Dan; Li, Sha; Wei, Xuetuan

2017-03-01

Two engineered Escherichia coli strains, DQ101 (MG1655 fadD - )/pDQTES and DQ101 (MG1655 fadD - )/pDQTESZ were constructed to investigate the free fatty acid production using ionic liquid-based acid- or enzyme-catalyzed bamboo hydrolysate as carbon source in this study. The plasmid, pDQTES, carrying an acyl-ACP thioesterase 'TesA of E. coli in pTrc99A was constructed firstly, and then (3R)-hydroxyacyl-ACP dehydratase was ligated after the TesA to give the plasmid pDQTESZ. These two strains exhibited efficient fatty acid production when glucose was used as the sole carbon source, with a final concentration of 2.45 and 3.32 g/L, respectively. The free fatty acid production of the two strains on xylose is not as efficient as that on glucose, which was 2.32 and 2.96 g/L, respectively. For mixed sugars, DQ101 (MG1655 fadD - )-based strains utilized glucose and pentose sequentially under the carbon catabolite repression (CCR) regulation. The highest total FFAs concentration from the mixed sugar culture reached 2.81 g/L by DQ101 (MG1655 fadD - )/pDQTESZ. Furthermore, when ionic liquid-based enzyme-catalyzed bamboo hydrolysate was used as the carbon source, the strain DQ101 (MG1655 fadD - )/pDQTESZ could produce 1.23 g/L FFAs with a yield of 0.13 g/g, and while it just produced 0.65 g/L free fatty acid with the ionic liquid-based acid-catalyzed bamboo hydrolysate as the feedstock. The results suggested that enzymatic catalyzed bamboo hydrolysate with ionic liquid pretreatment could serve as an efficient feedstock for free fatty acid production.

Choline-amino acid ionic liquids: past and recent achievements about the structure and properties of these really "green" chemicals.

PubMed

Gontrani, Lorenzo

2018-06-01

The structure of choline-amino acid ionic liquids, atoxic task-specific solvents composed of materials originated from renewable feedstocks, is reviewed in this letter. The varied and strong interactions that these liquids are capable of establishing are largely dependent on their structure and confer them outstanding solvating properties with respect to a large number of different solutes. Among the experimental methods capable of yielding structural insight, the energy-dispersive version of X-Ray diffraction, that uses the Bremsstrahlung radiation of the X-Ray tube, is a technique very well suited to investigate these liquid systems. The diffraction spectra of five choline-amino acid ionic liquids, recently measured, are reported and discussed; in particular, the presence or absence of the medium-range order pre-peak is related to the presence of polar groups within the amino acid side chain that destroys the hydrophobic interactions between aliphatic chains. In the final section, a recent example of choline-amino acid ionic liquids as for ancient paper preservation and two other interesting results are discussed at the end.

Superbase-derived protic ionic liquids

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

Dai, Sheng; Luo, Huimin; Baker, Gary A.

2013-09-03

Protic ionic liquids having a composition of formula (A.sup.-)(BH.sup.+) wherein A.sup.- is a conjugate base of an acid HA, and BH.sup.+ is a conjugate acid of a superbase B. In particular embodiments, BH.sup.+ is selected from phosphazenium species and guanidinium species encompassed, respectively, by the general formulas: ##STR00001## The invention is also directed to films and membranes containing these protic ionic liquids, with particular application as proton exchange membranes for fuel cells.

Extraction and Chromatographic Determination of Shikimic Acid in Chinese Conifer Needles with 1-Benzyl-3-methylimidazolium Bromide Ionic Liquid Aqueous Solutions

PubMed Central

Chen, Fengli; Hou, Kexin; Li, Shuangyang; Zu, Yuangang; Yang, Lei

2014-01-01

An ionic liquids-based ultrasound-assisted extraction (ILUAE) method was successfully developed for extracting shikimic acid from conifer needles. Eleven 1-alkyl-3-methylimidazolium ionic liquids with different cations and anions were investigated and 1-benzyl-3-methylimidazolium bromide solution was selected as the solvent. The conditions for ILUAE, including the ionic liquid concentration, ultrasound power, ultrasound time, and liquid-solid ratio, were optimized. The proposed method had good recovery (99.37%–100.11%) and reproducibility (RSD, n = 6; 3.6%). ILUAE was an efficient, rapid, and simple sample preparation technique that showed high reproducibility. Based on the results, a number of plant species, namely, Picea koraiensis, Picea meyeri, Pinus elliottii, and Pinus banksiana, were identified as among the best resources of shikimic acid. PMID:24782942

Confused ionic liquid ions--a "liquification" and dosage strategy for pharmaceutically active salts.

PubMed

Bica, Katharina; Rogers, Robin D

2010-02-28

We present a strategy to expand the liquid and compositional ranges of ionic liquids, specifically pharmaceutically active ionic liquids, by simple mixing with a solid acid or base to form oligomeric ions.

Ionic liquid as an electrolyte additive for high performance lead-acid batteries

NASA Astrophysics Data System (ADS)

Deyab, M. A.

2018-06-01

The performance of lead-acid battery is improved in this work by inhibiting the corrosion of negative battery electrode (lead) and hydrogen gas evolution using ionic liquid (1-ethyl-3-methylimidazolium diethyl phosphate). The results display that the addition of ionic liquid to battery electrolyte (5.0 M H2SO4 solution) suppresses the hydrogen gas evolution to very low rate 0.049 ml min-1 cm-2 at 80 ppm. Electrochemical studies show that the adsorption of ionic liquid molecules on the lead electrode surface leads to the increase in the charge transfer resistance and the decrease in the double layer capacitance. I also notice a noteworthy improvement of battery capacity from 45 mAh g-1 to 83 mAh g-1 in the presence of ionic liquid compound. Scanning electron microscopy and energy dispersive X-ray analysis confirm the adsorption of ionic liquid molecules on the battery electrode surface.

Effects of novel triple-stage antimalarial ionic liquids on lipid membrane models.

PubMed

Ferraz, Ricardo; Pinheiro, Marina; Gomes, Ana; Teixeira, Cátia; Prudêncio, Cristina; Reis, Salette; Gomes, Paula

2017-09-01

Primaquine-based ionic liquids, obtained by acid-base reaction between parent primaquine and cinnamic acids, were recently found as triple-stage antimalarial hits. These ionic compounds displayed significant activity against both liver- and blood-stage Plasmodium parasites, as well as against stage V P. falciparum parasites. Remarkably, blood-stage activity of the ionic liquids against both chloroquine-sensitive (3D7) and resistant (Dd2) P. falciparum strains was clearly superior to those of the respective covalent (amide) analogues and of parent primaquine. Having hypothesized that such behaviour might be ascribed to an enhanced ability of the ionic compounds to permeate into Plasmodium-infected erythrocytes, we have carried out a differential scanning calorimetry-based study of the interactions between the ionic liquids and membrane models. Results provide evidence, at the molecular level, that the primaquine-derived ionic liquids may contribute to an increased permeation of the parent drug into malaria-infected erythrocytes, which has relevant implications towards novel antimalarial approaches based on ionic liquids. Copyright © 2017 Elsevier Ltd. All rights reserved.

On the acid-base properties of humic acid in soil.

PubMed

Cooke, James D; Hamilton-Taylor, John; Tipping, Edward

2007-01-15

Humic acid was isolated from three contrasting organic-rich soils and acid-base titrations performed over a range of ionic strengths. Results obtained were unlike most humic acid data sets; they showed a greater ionic strength dependency at low pH than at high pH. Forward- and back-titrations with the base and acid revealed hysteresis, particularly at low pH. Previous authors attributed this type of hysteresis to humic acid aggregates-created during the isolation procedure-being redissolved during titration as the pH increased and regarded the results as artificial. However, forward- and back-titrations with organic-rich soils also demonstrated a similar hysteretic behavior. These observations indicate (i) that titrations of humic acid in aggregated form (as opposed to the more usual dissolved form) are more representative of the acid-base properties of humic acid in soil and (ii) that the ionic strength dependency of proton binding in humic acid is related to its degree of aggregation. Thus, the current use of models based on data from dissolved humic substances to predictthe acid-base properties of humic acid in soil under environmental conditions may be flawed and could substantially overestimate their acid buffering capacity.

Proton-conducting ionic liquid-based Proton Exchange Membrane Fuel Cell membranes: The key role of ionomer-ionic liquid interaction

NASA Astrophysics Data System (ADS)

Martinez, Mathieu; Molmeret, Yannick; Cointeaux, Laure; Iojoiu, Cristina; Leprêtre, Jean-Claude; El Kissi, Nadia; Judeinstein, Patrick; Sanchez, Jean-Yves

The paper deals with the synthesis and characterisation of proton-conducting ionic liquids (PCILs) and their polymer electrolytes obtained by blending modified Nafion membranes with different concentrations of PCILs. The PCILs are obtained by the neutralization of triethylamine with different organic acids. The first part of the paper studies the influence of acidity and acid structure on PCIL thermal and electrochemical performance, while the second part examines membrane conductivity and reveals it to depend more on PCIL structure than on its intrinsic conductivity. At 130 °C, conductivities exceeding 10 mS cm -1 were obtained in fully anhydrous conditions.

Lunar Oxygen Production and Metals Extraction Using Ionic Liquids

NASA Technical Reports Server (NTRS)

Marone, Matthew; Paley, Mark Steven; Donovan, David N.; Karr, Laurel J.

2009-01-01

Initial results indicate that ionic liquids are promising media for the extraction of oxygen from lunar regolith. IL acid systems can solubilize regolith and produce water with high efficiency. IL electrolytes are effective for water electrolysis, and the spent IL acid media are capable of regeneration.

Ionic liquids and ionic liquid acids with high temperature stability for fuel cell and other high temperature applications, method of making and cell employing same

DOEpatents

Angell, C Austen [Mesa, AZ; Xu, Wu [Broadview Heights, OH; Belieres, Jean-Philippe [Chandler, AZ; Yoshizawa, Masahiro [Tokyo, JP

2011-01-11

Disclosed are developments in high temperature fuel cells including ionic liquids with high temperature stability and the storage of inorganic acids as di-anion salts of low volatility. The formation of ionically conducting liquids of this type having conductivities of unprecedented magnitude for non-aqueous systems is described. The stability of the di-anion configuration is shown to play a role in the high performance of the non-corrosive proton-transfer ionic liquids as high temperature fuel cell electrolytes. Performance of simple H.sub.2(g) electrolyte/O.sub.2(g) fuel cells with the new electrolytes is described. Superior performance both at ambient temperature and temperatures up to and above 200.degree. C. are achieved. Both neutral proton transfer salts and the acid salts with HSO.sup.-.sub.4 anions, give good results, the bisulphate case being particularly good at low temperatures and very high temperatures. The performance of all electrolytes is improved by the addition of a small amount of involatile base of pK.sub.a value intermediate between those of the acid and base that make the bulk electrolyte. The preferred case is the imidazole-doped ethylammonium hydrogensulfate which yields behavior superior in all respects to that of the industry standard phosphoric acid electrolyte.

Chemical Kinetics Interpretation of Hypergolicity of Ionic Liquid-Based Systems

DTIC Science & Technology

2009-04-01

acid (WFNA) mixtures 6 4. Thermochemistry of imidazoles, triazoles and tetrazoles 8 5. Thermochemistry of compounds formed...reactivity of gaseous mixtures formed above ionic liquids (ILs) when mixed with white fuming nitric acid (WFNA). After a general introduction on the...replacement for NTO is also of interest but probably less crucial. For instance, NTO could be replaced by nitric acid (or by any other suitable

Simultaneous extraction and HPLC determination of 3-indole butyric acid and 3-indole acetic acid in pea plant by using ionic liquid-modified silica as sorbent.

PubMed

Sheikhian, Leila; Bina, Sedigheh

2016-01-15

In this study, ionic liquid-modified silica was used as sorbent for simultaneous extraction and preconcentration of 3-indole butyric acid and 3-indole acetic acid in pea plants. The effect of some parameters such as pH and ionic strength of sample solution, amount of sorbent, flow rate of aqueous sample solution and eluent solution, concentration of eluent solution, and temperature were studied for each hormone solution. Percent extraction of 3-indole butyric acid and 3-indole acetic acid was strongly affected by pH of aqueous sample solution. Ionic strength of aqueous phase and temperature showed no serious effects on extraction efficiency of studied plant hormones. Obtained breakthrough volume was 200mL for each of studied hormones. Preconcentration factor for spectroscopic and chromatographic determination of studied hormones was 100 and 4.0×10(3) respectively. Each solid sorbent phase was reusable for almost 10 times of extraction/stripping procedure. Relative standard deviations of extraction/stripping processes of 3-indole butyric acid and 3-indole acetic acid were 2.79% and 3.66% respectively. The calculated limit of detections for IBA and IAA were 9.1×10(-2)mgL(-1) and 1.6×10(-1)mgL(-1) respectively. Copyright © 2015 Elsevier B.V. All rights reserved.

Extensive structural change of the envelope protein of dengue virus induced by a tuned ionic strength: conformational and energetic analyses

NASA Astrophysics Data System (ADS)

Degrève, Léo; Fuzo, Carlos A.; Caliri, Antonio

2012-12-01

The Dengue has become a global public health threat, with over 100 million infections annually; to date there is no specific vaccine or any antiviral drug. The structures of the envelope (E) proteins of the four known serotype of the dengue virus (DENV) are already known, but there are insufficient molecular details of their structural behavior in solution in the distinct environmental conditions in which the DENVs are submitted, from the digestive tract of the mosquito up to its replication inside the host cell. Such detailed knowledge becomes important because of the multifunctional character of the E protein: it mediates the early events in cell entry, via receptor endocytosis and, as a class II protein, participates determinately in the process of membrane fusion. The proposed infection mechanism asserts that once in the endosome, at low pH, the E homodimers dissociate and insert into the endosomal lipid membrane, after an extensive conformational change, mainly on the relative arrangement of its three domains. In this work we employ all-atom explicit solvent Molecular Dynamics simulations to specify the thermodynamic conditions in that the E proteins are induced to experience extensive structural changes, such as during the process of reducing pH. We study the structural behavior of the E protein monomer at acid pH solution of distinct ionic strength. Extensive simulations are carried out with all the histidine residues in its full protonated form at four distinct ionic strengths. The results are analyzed in detail from structural and energetic perspectives, and the virtual protein movements are described by means of the principal component analyses. As the main result, we found that at acid pH and physiological ionic strength, the E protein suffers a major structural change; for lower or higher ionic strengths, the crystal structure is essentially maintained along of all extensive simulations. On the other hand, at basic pH, when all histidine residues are in the unprotonated form, the protein structure is very stable for ionic strengths ranging from 0 to 225 mM. Therefore, our findings support the hypothesis that the histidines constitute the hot points that induce configurational changes of E protein in acid pH, and give extra motivation to the development of new ideas for antivirus compound design.

EFFECTS OF PH, SOLID/SOLUTION RATIO, IONIC STRENGTH, AND ORGANIC ACIDS ON PB AND CD SOPRTION ON KAOLINITE

EPA Science Inventory

Potentiometric and ion-selective electrode titrations together with batch sorption/desorption experiments, were performed to explain the aqueous and surface complexation reactions between kaolinite, Pb, Cd and three organic acids. Variables included pH, ionic strength, metal conc...

Amino acid ionic liquids as chiral ligands in ligand-exchange chiral separations.

PubMed

Liu, Qian; Wu, Kangkang; Tang, Fei; Yao, Lihua; Yang, Fei; Nie, Zhou; Yao, Shouzhuo

2009-09-28

Recently, amino acid ionic liquids (AAILs) have attracted much research interest. In this paper, we present the first application of AAILs in chiral separation based on the chiral ligand exchange principle. By using 1-alkyl-3-methylimidazolium L-proline (L-Pro) as a chiral ligand coordinated with copper(II), four pairs of underivatized amino acid enantiomers-dl-phenylalanine (dl-Phe), dl-histidine (dl-His), dl-tryptophane (dl-Trp), and dl-tyrosine (dl-Tyr)-were successfully separated in two major chiral separation techniques, HPLC and capillary electrophoresis (CE), with higher enantioselectivity than conventionally used amino acid ligands (resolution (R(s))=3.26-10.81 for HPLC; R(s)=1.34-4.27 for CE). Interestingly, increasing the alkyl chain length of the AAIL cation remarkably enhanced the enantioselectivity. It was inferred that the alkylmethylimidazolium cations and L-Pro form ion pairs on the surface of the stationary phase or on the inner surface of the capillary. The ternary copper complexes with L-Pro are consequently attached to the support surface, thus inducing an ion-exchange type of retention for the dl-enantiomers. Therefore, the AAIL cation plays an essential role in the separation. This work demonstrates that AAILs are good alternatives to conventional amino acid ligands for ligand-exchange-based chiral separation. It also reveals the tremendous application potential of this new type of task-specific ILs.

Furfural production using ionic liquids: A review.

PubMed

Peleteiro, Susana; Rivas, Sandra; Alonso, José Luis; Santos, Valentín; Parajó, Juan Carlos

2016-02-01

Furfural, a platform chemical with a bright future, is commercially obtained by acidic processing of xylan-containing biomass in aqueous media. Ionic liquids (ILs) can be employed in processed for furfural manufacture as additives, as catalysts and/or as reaction media. Depending on the IL utilized, externally added catalysts (usually, Lewis acids, Brönsted acids and/or solid acid catalysts) can be necessary to achieve high reaction yields. Oppositely, acidic ionic liquids (AILs) can perform as both solvents and catalysts, enabling the direct conversion of suitable substrates (pentoses, pentosans or xylan-containing biomass) into furfural. Operating in IL-containing media, the furfural yields can be improved when the product is continuously removed along the reaction (for example, by stripping or extraction), to avoid unwanted side-reactions leading to furfural consumption. These topics are reviewed, as well as the major challenges involved in the large scale utilization of ILs for furfural production. Copyright © 2015 Elsevier Ltd. All rights reserved.

Thermophysical Properties of Energetic Ionic Liquids/Nitric Acid Mixtures: Insights from Molecular Dynamics Simulations

DTIC Science & Technology

2013-01-01

W L. Physical properties of concentrated nitric acid . UNT Digital Library. http://digital.library.unt.edu/ark:/67531/metadc56640/.) 23 M. Engelmann... Nitric Acid Mixtures: Insights from Molecular Dynamics Simulations 5a. CONTRACT NUMBER FA9300-11-C-3012 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER...Rev. 8-98) Prescribed by ANSI Std. 239.18 1     Thermophysical  Properties  of  Energetic  Ionic  Liquids/ Nitric   Acid

Particle self-assembly at ionic liquid-based interfaces.

PubMed

Frost, Denzil S; Nofen, Elizabeth M; Dai, Lenore L

2014-04-01

This review presents an overview of the nature of ionic liquid (IL)-based interfaces and self-assembled particle morphologies of IL-in-water, oil- and water-in-IL, and novel IL-in-IL Pickering emulsions with emphasis on their unique phenomena, by means of experimental and computational studies. In IL-in-water Pickering emulsions, particles formed monolayers at ionic liquid-water interfaces and were close-packed on fully covered emulsion droplets or aggregated on partially covered droplets. Interestingly, other than equilibrating at the ionic liquid-water interfaces, microparticles with certain surface chemistries were extracted into the ionic liquid phase with a high efficiency. These experimental findings were supported by potential of mean force calculations, which showed large energy drops as hydrophobic particles crossed the interface into the IL phase. In the oil- and water-in-IL Pickering emulsions, microparticles with acidic surface chemistries formed monolayer bridges between the internal phase droplets rather than residing at the oil/water-ionic liquid interfaces, a significant deviation from traditional Pickering emulsion morphology. Molecular dynamics simulations revealed aspects of the mechanism behind this bridging phenomenon, including the role of the droplet phase, surface chemistry, and inter-particle film. Novel IL-in-IL Pickering emulsions exhibited an array of self-assembled morphologies including the previously observed particle absorption and bridging phenomena. The appearance of these morphologies depended on the particle surface chemistry as well as the ILs used. The incorporation of particle self-assembly with ionic liquid science allows for new applications at the intersection of these two fields, and have the potential to be numerous due to the tunability of the ionic liquids and particles incorporated, as well as the particle morphology by combining certain groups of particle surface chemistry, IL type (protic or aprotic), and whether oil or water is incorporated. © 2013.

Surface confined ionic liquid as a stationary phase for HPLC

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

Wang, Qian; Baker, Gary A; Baker, Sheila N

Trimethoxysilane ionosilane derivatives of room temperature ionic liquids based on alkylimidazolium bromides were synthesized for attachment to silica support material. The derivatives 1-methyl-3-(trimethoxysilylpropyl)imidazolium bromide and 1-butyl-3-(trimethoxysilylpropyl)imidazolium bromide were used to modify the surface of 3 {micro}m diameter silica particles to act as the stationary phase for HPLC. The modified particles were characterized by thermogravimetric analysis (TGA) and {sup 13}C and {sup 29}Si NMR spectroscopies. The surface modification procedure rendered particles with a surface coverage of 0.84 {micro}mol m{sup -2} for the alkylimidazolium bromide. The ionic liquid moiety was predominantly attached to the silica surface through two siloxane bonds of themore » ionosilane derivative (63%). Columns packed with the modified silica material were tested under HPLC conditions. Preliminary evaluation of the stationary phase for HPLC was performed using aromatic carboxylic acids as model compounds. The separation mechanism appears to involve multiple interactions including ion exchange, hydrophobic interaction, and other electrostatic interactions.« less

Acid-Base Chemistry of White Wine: Analytical Characterisation and Chemical Modelling

PubMed Central

Prenesti, Enrico; Berto, Silvia; Toso, Simona; Daniele, Pier Giuseppe

2012-01-01

A chemical model of the acid-base properties is optimized for each white wine under study, together with the calculation of their ionic strength, taking into account the contributions of all significant ionic species (strong electrolytes and weak one sensitive to the chemical equilibria). Coupling the HPLC-IEC and HPLC-RP methods, we are able to quantify up to 12 carboxylic acids, the most relevant substances responsible of the acid-base equilibria of wine. The analytical concentration of carboxylic acids and of other acid-base active substances was used as input, with the total acidity, for the chemical modelling step of the study based on the contemporary treatment of overlapped protonation equilibria. New protonation constants were refined (L-lactic and succinic acids) with respect to our previous investigation on red wines. Attention was paid for mixed solvent (ethanol-water mixture), ionic strength, and temperature to ensure a thermodynamic level to the study. Validation of the chemical model optimized is achieved by way of conductometric measurements and using a synthetic “wine” especially adapted for testing. PMID:22566762

Acid-base chemistry of white wine: analytical characterisation and chemical modelling.

PubMed

Prenesti, Enrico; Berto, Silvia; Toso, Simona; Daniele, Pier Giuseppe

2012-01-01

A chemical model of the acid-base properties is optimized for each white wine under study, together with the calculation of their ionic strength, taking into account the contributions of all significant ionic species (strong electrolytes and weak one sensitive to the chemical equilibria). Coupling the HPLC-IEC and HPLC-RP methods, we are able to quantify up to 12 carboxylic acids, the most relevant substances responsible of the acid-base equilibria of wine. The analytical concentration of carboxylic acids and of other acid-base active substances was used as input, with the total acidity, for the chemical modelling step of the study based on the contemporary treatment of overlapped protonation equilibria. New protonation constants were refined (L-lactic and succinic acids) with respect to our previous investigation on red wines. Attention was paid for mixed solvent (ethanol-water mixture), ionic strength, and temperature to ensure a thermodynamic level to the study. Validation of the chemical model optimized is achieved by way of conductometric measurements and using a synthetic "wine" especially adapted for testing.

Covalent Immobilization of Cellulase Using Magnetic Poly(ionic liquid) Support: Improvement of the Enzyme Activity and Stability.

PubMed

Hosseini, Seyed Hassan; Hosseini, Seyedeh Ameneh; Zohreh, Nasrin; Yaghoubi, Mahshid; Pourjavadi, Ali

2018-01-31

A magnetic nanocomposite was prepared by entrapment of Fe 3 O 4 nanoparticles into the cross-linked ionic liquid/epoxy type polymer. The resulting support was used for covalent immobilization of cellulase through the reaction with epoxy groups. The ionic surface of the support improved the adsorption of enzyme, and a large amount of enzyme (106.1 mg/g) was loaded onto the support surface. The effect of the presence of ionic monomer and covalent binding of enzyme was also investigated. The structure of support was characterized by various instruments such as FT-IR, TGA, VSM, XRD, TEM, SEM, and DLS. The activity and stability of immobilized cellulase were investigated in the prepared support. The results showed that the ionic surface and covalent binding of enzyme onto the support improved the activity, thermal stability, and reusability of cellulase compared to free cellulase.

Reversible and strong immobilization of proteins by ionic exchange on supports coated with sulfate-dextran.

PubMed

Fuentes, Manuel; Pessela, Benevides C C; Maquiese, Jorgette V; Ortiz, Claudia; Segura, Rosa L; Palomo, Jose M; Abian, Olga; Torres, Rodrigo; Mateo, Cesar; Fernández-Lafuente, Roberto; Guisán, J M

2004-01-01

New and strong ionic exchange resins have been prepared by the simple and rapid ionic adsorption of anionic polymers (sulfate-dextran) on porous supports activated with the opposite ionic group (DEAE/MANAE). Ionic exchange properties of such composites were strongly dependent on the size of the ionic polymers as well as on the conditions of the ionic coating of the solids with the ionic polymers (optimal conditions were 400 mg of sulfate-dextran 5000 kDa per gram of support). Around 80% of the proteins contained in crude extracts from Escherichia coli and Acetobacter turbidans could be adsorbed on these porous composites even at pH 7. This interaction was stronger than that using conventional carboxymethyl cellulose (CMC) and even others such as supports coated with aspartic-dextran polymer. By means of the sequential use of the new supports and supports coated with polyethyleneimine (PEI), all proteins from crude extracts could be immobilized. In fact, a large percentage (over 50%) could be immobilized on both supports. Finally, some industrially relevant enzymes (beta-galactosidases from Aspergillus oryzae, Kluyveromyces lactis, and Thermussp. strain T2, lipases from Candida antarctica A and B, Candida rugosa, Rhizomucor miehei, and Rhyzopus oryzae and bovine pancreas trypsin and chymotrypsin) have been immobilized on these supports with very high activity recoveries and immobilization rates. After enzyme inactivation, the protein could be fully desorbed from the support, and then the support could be reused for several cycles. Moreover, in some instances the enzyme stability was significantly improved, mainly in the presence of organic solvents, perhaps as a consequence of the highly hydrophilic microenvironment of the support.

Ionic Strength Effect on the Rate of Reduction of Hexacyanoferrate (III) by Ascorbic Acid: A Physical Chemistry Laboratory Experiment.

ERIC Educational Resources Information Center

Watkins, Kenneth W.; Olson, June A.

1980-01-01

Describes a physical chemistry experiment that allows students to test the effect of ionic strength on the rates of a reaction between ions. The reduction of hexacyanoferrate III by ascorbic acid is detailed. Comparisons with the iodine clock reaction are made. (CS)

Organosilica Membrane with Ionic Liquid Properties for Separation of Toluene/H₂ Mixture.

PubMed

Hirota, Yuichiro; Maeda, Yohei; Yamamoto, Yusuke; Miyamoto, Manabu; Nishiyama, Norikazu

2017-08-03

In this study, we present a new concept in chemically stabilized ionic liquid membranes: an ionic liquid organosilica (ILOS) membrane, which is an organosilica membrane with ionic liquid-like properties. A silylated ionic liquid was used as a precursor for synthesis. The permselectivity, permeation mechanism, and stability of the membrane in the H₂/toluene binary system were then compared with a supported ionic liquid membrane. The membrane showed a superior separation factor of toluene/H₂ (>17,000) in a binary mixture system based on a solution-diffusion mechanism with improved durability over the supported ionic liquid membrane.

Electrochemically stable electrolytes

DOEpatents

Angell, Charles Austen; Zhang, Sheng-Shui; Xu, Kang

1999-01-01

This invention relates generally to inorganic ionic liquids which function as electrolytes and do not crystallize at ambient temperature. More specifically, this invention is directed to quasi-salt inorganic ionic liquids which comprise the reaction product of a strong Lewis acid with an inorganic halide-donating molecule. This invention is further directed to quasi-salt inorganic ionic liquid mixtures which comprise combinations of electrolyte additives and quasi-salt inorganic ionic liquids. These quasi-salt inorganic ionic liquid mixtures are useful electrolytes.

Electrochemically stable electrolytes

DOEpatents

Angell, C.A.; Zhang, S.S.; Xu, K.

1999-01-05

This invention relates generally to inorganic ionic liquids which function as electrolytes and do not crystallize at ambient temperature. More specifically, this invention is directed to quasi-salt inorganic ionic liquids which comprise the reaction product of a strong Lewis acid with an inorganic halide-donating molecule. This invention is further directed to quasi-salt inorganic ionic liquid mixtures which comprise combinations of electrolyte additives and quasi-salt inorganic ionic liquids. These quasi-salt inorganic ionic liquid mixtures are useful electrolytes. 16 figs.

Ionic Liquid as a Solvent and Catalyst for Acylation of Maltodextrin

USDA-ARS?s Scientific Manuscript database

Catalyst-free esterification of maltodextrin was carried out in ionic liquid. Stearate esters of maltodextrin were obtained in various degree of substitution (DS) when vinyl stearate or stearic acid was heated with maltodextrin in ionic liquid, 1-butyl-3-methylimidazolium cyanamide (bmim[dca]). Re...

Nanoporous array anodic titanium-supported co-polymeric ionic liquids as high performance solid-phase microextraction sorbents for hydrogen bonding compounds.

PubMed

Jia, Jing; Liang, Xiaojing; Wang, Licheng; Guo, Yong; Liu, Xia; Jiang, Shengxiang

2013-12-13

A nanoporous array anodic titanium-supported co-polymeric ionic liquids (NAAT/PILs) solid-phase microextraction (SPME) fiber was prepared in situ on the titanium wire. NAAT was selected as the substrate, in view of its high surface-to-volume ratio, easy preparation, mechanical stability, and rich titanol groups on its surface which can anchor silica coupling agent containing vinyl and then introduce ionic liquid copolymers as sorbents. In this work, 1-vinyl-3-nonanol imidazolium bromide ([C9OHVIm]Br) and 1,4-di(3-vinylimidazolium) butane dibromide ([(VIM)2C4]2[Br]) were synthesized and used as monomer and crosslinker, respectively. Extraction properties of the NAAT/PILs fiber for polar alcohols and volatile fatty acids (VFAs) in aqueous matrix were examined using gaseous sampling-SPME (GS-SPME) and headspace SPME (HS-SPME) mode, respectively. Combining the superior properties of NAAT substrate and the strong hydrogen bond interaction of PILs to polar compounds, the NAAT/PILs SPME fiber showed much higher adsorption affinity to aliphatic alcohols than bare NAAT and pure PILs fibers. The detection limits (LOD) of established GS-SPME-GC-FID method are in the range of 0.35-17.30ngL(-1) with a linear range from 0.01 to 500ngmL(-1). Also, it showed high extraction performance toward volatile fatty acids (VFAs) compounds from aqueous matrix. Under the optimized SPME conditions, wide linear ranges were obtained with correlation coefficients (R(2)) greater than 0.99 and limits of detection were in the range of 0.85-8.74ngL(-1). Moreover, real-world samples were analyzed and good results were obtained. Copyright © 2013. Published by Elsevier B.V.

Sequestration of U(VI) from Acidic, Alkaline, and High Ionic-Strength Aqueous Media by Functionalized Magnetic Mesoporous Silica Nanoparticles: Capacity and Binding Mechanisms

EPA Science Inventory

Uranium (VI) exhibits little adsorption onto sediment minerals in acidic, alkaline or high ionic-strength aqueous media that often occur in U mining or contaminated sites, which makes U(VI) very mobile and difficult to sequester. In this work, magnetic mesoporous silica nanoparti...

Solid-state supramolecular architectures formed by co-crystallization of melamine and 2-, 3- and 4-fluorophenylacetic acids

NASA Astrophysics Data System (ADS)

Perpétuo, Genivaldo Julio; Janczak, Jan

2018-01-01

A family of supramolecular complexes of melamine with fluorophenylacetic acid isomers using solvent-assisted and evaporation-based techniques has been prepared. Crystallization of melamine with 2-fluorophenylacetic acid yield hydrated ionic supramolecular complex (1), whereas crystallization of melamine with 3- and 4-fluorophenylacetic acids leads to formation of neutral supramolecular complexes (2, 3), all with base to acid ratio of 1:2. The supramolecular assembly is driven by the noncovalent interactions, most commonly by the hydrogen bonds. The components of the crystal 1 interact via Nsbnd H⋯O and Osbnd H⋯N hydrogen bonds with R22(8) and R32(10) graphs forming ionic supramolecular complex, whereas the components in the crystals 2 and 3 interact with a graph of R22(8) forming neutral supramolecular complexes. The singly protonated melamin-1-ium residues in 1 interact each other via a pair of Nsbnd H⋯N hydrogen bonds forming one dimensional chains along [-110] that interact via Nsbnd H⋯O with deprotonated and neutral 2-fluorophenylacetic acid units and water molecules forming ribbon. In 2 and 3 co-crystals the melamine interacts with 3- and 4-fluorophenylacetic acids via a pair of Nsbnd H⋯O hydrogen bonds forming pseudo one-dimensional supramolecular chains along [010] direction. Hirshfeld surface and analysis of 2D fingerprint plots have been analysed both quantitatively and qualitatively interactions that governing the supramolecular organisation. The IR and Raman vibrational characterization of the supramolecular complexes 1-3 was supported by the spectra of their deuterated analogues.

Modeling solubility, acid-base properties and activity coefficients of amoxicillin, ampicillin and (+)6-aminopenicillanic acid, in NaCl(aq) at different ionic strengths and temperatures.

PubMed

Crea, Francesco; Cucinotta, Daniela; De Stefano, Concetta; Milea, Demetrio; Sammartano, Silvio; Vianelli, Giuseppina

2012-11-20

The total solubility of three penicillin derivatives was determined, in pure water and NaCl aqueous solutions at different salt concentrations (from ∼0.15 to 1.0 mol L(-1) for ampicillin and amoxicillin, and from ∼0.05 to 2.0 mol L(-1) for (+)6-aminopenicillanic acid), using the shake-flask method for generating the saturated solutions, followed by potentiometric analysis. The knowledge of the pH of solubilization and of the protonation constants determined in the same experimental conditions, allowed us to calculate, by means of the mass balance equations, the solubility of the neutral species at different ionic strength values, to model its dependence on the salt concentration and to determine the corresponding values at infinite dilution. The salting parameter and the activity coefficients of the neutral species were calculated by the Setschenow equation. The protonation constants of ampicillin and amoxicillin, determined at different temperatures (from T=288.15 to 318.15K), from potentiometric and spectrophotometric measurements, were used to calculate, by means of the Van't Hoff equation, the temperature coefficients at different ionic strength values and the corresponding protonation entropies. The protonation enthalpies of the (+)6-aminopenicillanic acid were determined by isoperibol calorimetric titrations at T=298.15K and up to I=2.0 mol L(-1). The dependence of the protonation constants on ionic strength was modeled by means of the Debye-Hückel and SIT (Specific ion Interaction Theory) approaches, and the specific interaction parameters of the ionic species were determined. The hydrolysis of the β-lactam ring was studied by spectrophotometric and H NMR investigations as a function of pH, ionic strength and time. Potentiometric measurements carried out on the hydrolyzed (+)6-aminopenicillanic acid allowed us to highlight that the opened and the closed β-lactam forms of the (+)6-aminopenicillanic acid have quite different acid-base properties. An analysis of literature solubility, protonation constants, enthalpies and activity coefficients is reported too. Copyright © 2012 Elsevier B.V. All rights reserved.

Ionic Ckonductivity and Glass Transition of Phosphoric Acids

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

Wang, Yangyang; Lane, Nathan A; Sun, Che-Nan

2013-01-01

Here we report the low-temperature dielectric and viscoelastic properties of phosphoric acids in the range of H2O:P2O5 1.5 5. Both dielectric and viscosity measurements allow us to determine the glass-transition temperatures of phosphoric acids. The obtained glass-transition temperatures are in good agreement with previous differential scanning calorimetric measurements. Moreover, our analysis reveals moderate decoupling of ionic conductivity from structural relaxation in the vicinity of the glass transition.

Ionic conductivity and glass transition of phosphoric acids

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

Wang, Yangyang; Lane, Nathan A; Sun, Che-Nan

2013-01-01

Here we report the low-temperature dielectric and viscoelastic properties of phosphoric acids in the range of H2O:P2O5 1.5 5. Both dielectric and viscosity measurements allow us to determine the glass-transition temperatures of phosphoric acids. The obtained glass-transition temperatures are in good agreement with previous differential scanning calorimetric measurements. Moreover, our analysis reveals moderate decoupling of ionic conductivity from structural relaxation in the vicinity of the glass transition.

Optimization of enzymatic esterification of dihydrocaffeic acid with hexanol in ionic liquid using response surface methodology.

PubMed

Gholivand, Somayeh; Lasekan, Ola; Tan, Chin Ping; Abas, Faridah; Wei, Leong Sze

2017-05-26

Developing an efficient lipophilization reaction system for phenolic derivatives could enhance their applications in food processing. Low solubility of phenolic acids reduces the efficiency of phenolic derivatives in most benign enzyme solvents. The conversion of phenolic acids through esterification alters their solubility and enhances their use as food antioxidant additives as well as their application in cosmetics. This study has shown that lipase-catalyzed esterification of dihydrocaffeic acid with hexanol in ionic liquid (1-butyl-3-methylimidazoliumbis (trifluoromethylsulfonyl) imide) was the best approach for esterification reaction. In order to achieve the maximum yield, the process was optimized by response surface methodology (RSM) based on a five-level and four independent variables such as: dosage of enzyme; hexanol/dihydrocaffeic acid mole ratio; temperature and reaction time. The optimum esterification condition (Y = 84.4%) was predicted to be obtained at temperature of 39.4 °C, time of 77.5 h dosage of enzyme at 41.6% and hexanol/dihydrocaffeic acid mole ratio of 2.1. Finally, this study has produced an efficient enzymatic esterification method for the preparation of hexyl dihydrocaffeate in vitro using a lipase in an ionic liquid system. Concentration of hexanol was the most significant (p < 0.05) independent variable that influenced the yield of hexyl dihydrocaffeate. Graphical abstract Synthesis of different Hexyl dihydrocaffeates in ionic liquid.

Flow-Tube Investigations of Hypergolic Reactions of a Dicyanamide Ionic Liquid Via Tunable Vacuum Ultraviolet Aerosol Mass Spectrometry.

PubMed

Chambreau, Steven D; Koh, Christine J; Popolan-Vaida, Denisia M; Gallegos, Christopher J; Hooper, Justin B; Bedrov, Dmitry; Vaghjiani, Ghanshyam L; Leone, Stephen R

2016-10-07

The unusually high heats of vaporization of room-temperature ionic liquids (RTILs) complicate the utilization of thermal evaporation to study ionic liquid reactivity. Although effusion of RTILs into a reaction flow-tube or mass spectrometer is possible, competition between vaporization and thermal decomposition of the RTIL can greatly increase the complexity of the observed reaction products. In order to investigate the reaction kinetics of a hypergolic RTIL, 1-butyl-3-methylimidazolium dicyanamide (BMIM + DCA - ) was aerosolized and reacted with gaseous nitric acid, and the products were monitored via tunable vacuum ultraviolet photoionization time-of-flight mass spectrometry at the Chemical Dynamics Beamline 9.0.2 at the Advanced Light Source. Reaction product formation at m/z 42, 43, 44, 67, 85, 126, and higher masses was observed as a function of HNO 3 exposure. The identities of the product species were assigned to the masses on the basis of their ionization energies. The observed exposure profile of the m/z 67 signal suggests that the excess gaseous HNO 3 initiates rapid reactions near the surface of the RTIL aerosol. Nonreactive molecular dynamics simulations support this observation, suggesting that diffusion within the particle may be a limiting step. The mechanism is consistent with previous reports that nitric acid forms protonated dicyanamide species in the first step of the reaction.

Basicity of pyridine and some substituted pyridines in ionic liquids.

PubMed

Angelini, Guido; De Maria, Paolo; Chiappe, Cinzia; Fontana, Antonella; Pierini, Marco; Siani, Gabriella

2010-06-04

The equilibrium constants for ion pair formation of some pyridines have been evaluated by spectrophotometric titration with trifluoroacetic acid in different ionic liquids. The basicity order is the same in ionic liquids and in water. The substituent effect on the equilibrium constant has been discussed in terms of the Hammett equation. Pyridine basicity appears to be less sensitive to the substituent effect in ionic liquids than in water.

Removal of natural organic matter by titanium tetrachloride: The effect of total hardness and ionic strength.

PubMed

Zhao, Y X; Shon, H K; Phuntsho, S; Gao, B Y

2014-02-15

This study is the first attempt to investigate the effect of total hardness and ionic strength on coagulation performance and the floc characteristics of titanium tetrachloride (TiCl4). Membrane fouling under different total hardness and ionic strength conditions was also evaluated during a coagulation-ultrafiltration (C-UF) hybrid process. Coagulation experiments were performed with two simulated waters, using humic acid (HA, high molecular weight) and fulvic acid (FA, relatively low molecular weight), respectively, as model natural organic matter (NOM). Results show that both particle and organic matter removal can be enhanced by increasing total hardness and ionic strength. Floc characteristics were significantly influenced by total hardness and ionic strength and were improved in terms of floc size, growth rate, strength, recoverability and compactness. The results of the UF tests show that the pre-coagulation with TiCl4 significantly improves the membrane permeate fluxes. Under different total hardness and ionic strength conditions, the membrane permeate flux varied according to both NOM and floc characteristics. The increase in total hardness and ionic strength improved the membrane permeate flux in the case of HA simulated water treatment. Copyright © 2014 Elsevier Ltd. All rights reserved.

Transport and Retention of TiO2 Rutile Nanoparticles in Saturated Porous Media: Influence of Solution pH, Ionic Strength, and the Presence of Humic Acid

EPA Science Inventory

The influence of solution pH, ionic strength, and varying concentrations of the Suwannee River Humic Acid (SRHA) on the transport of titanium dioxide (TiO2, rutile) nanoparticle aggregates (nTiO2) in saturated porous media was investigated through systematically examining the tra...

Binding mechanisms for histamine and agmatine ligands in plasmid deoxyribonucleic acid purifications.

PubMed

Sousa, Ângela; Pereira, Patrícia; Sousa, Fani; Queiroz, João A

2014-10-31

Histamine and agmatine amino acid derivatives were immobilized into monolithic disks, in order to combine the specificity and selectivity of the ligand with the high mass transfer and binding capacity offered by monolithic supports, to purify potential plasmid DNA biopharmaceuticals. Different elution strategies were explored by changing the type and salt concentration, as well as the pH, in order to understand the retention pattern of different plasmids isoforms The pVAX1-LacZ supercoiled isoform was isolated from a mixture of pDNA isoforms by using NaCl increasing stepwise gradient and also by ammonium sulfate decreasing stepwise gradient, in both histamine and agmatine monoliths. Acidic pH in the binding buffer mainly strengthened ionic interactions with both ligands in the presence of sodium chloride. Otherwise, for histamine ligand, pH values higher than 7 intensified hydrophobic interactions in the presence of ammonium sulfate. In addition, circular dichroism spectroscopy studies revealed that the binding and elution chromatographic conditions, such as the combination of high ionic strength with extreme pH values can reversibly influence the structural stability of the target nucleic acid. Therefore, ascending sodium chloride gradients with pH manipulation can be preferable chromatographic conditions to be explored in the purification of plasmid DNA biopharmaceuticals, in order to avoid the environmental impact of ammonium sulfate. Copyright © 2014. Published by Elsevier B.V.

Development and optimization of a naphthoic acid-based ionic liquid as a "non-organic solvent microextraction" for the determination of tetracycline antibiotics in milk and chicken eggs.

PubMed

Gao, Jiajia; Wang, Hui; Qu, Jingang; Wang, Huili; Wang, Xuedong

2017-01-15

In traditional ionic liquids (ILs)-based microextraction, ILs are often used as extraction and dispersive solvents; however, their functional effects are not fully utilized. Herein, we developed a novel ionic liquid 1-butyl-3-methylimidazolium naphthoic acid salt ([C4MIM][NPA]) with strong acidity. It was used as a mixed dispersive solvent with conventional [C2MIM][BF4] in "functionalized ionic liquid-based non-organic solvent microextraction (FIL-NOSM)" for determination of tetracycline antibiotics (TCs) in milk and eggs. Utilization of [C4MIM][NPA] in FIL-NOSM method increased extraction recoveries (ERs) of TCs by more than 20% and eliminated the pH adjustment step because of its strong acidity. Under optimized conditions based on central composite design, the ERs of four TCs were 94.1-102.1%, and the limitsofdetection were 0.08-1.12μgkg(-1) in milk and egg samples. This proposed method provides high extraction efficiency, less pretreatment time and requires non-organic solvents for determination of trace TC concentrations in complex animal-based food matrices. Copyright © 2016 Elsevier Ltd. All rights reserved.

Two-Stage Conversion of High Free Fatty Acid Jatropha curcas Oil to Biodiesel Using Brønsted Acidic Ionic Liquid and KOH as Catalysts

PubMed Central

Das, Subrata; Thakur, Ashim Jyoti; Deka, Dhanapati

2014-01-01

Biodiesel was produced from high free fatty acid (FFA) Jatropha curcas oil (JCO) by two-stage process in which esterification was performed by Brønsted acidic ionic liquid 1-(1-butylsulfonic)-3-methylimidazolium chloride ([BSMIM]Cl) followed by KOH catalyzed transesterification. Maximum FFA conversion of 93.9% was achieved and it reduced from 8.15 wt% to 0.49 wt% under the optimum reaction conditions of methanol oil molar ratio 12 : 1 and 10 wt% of ionic liquid catalyst at 70°C in 6 h. The ionic liquid catalyst was reusable up to four times of consecutive runs under the optimum reaction conditions. At the second stage, the esterified JCO was transesterified by using 1.3 wt% KOH and methanol oil molar ratio of 6 : 1 in 20 min at 64°C. The yield of the final biodiesel was found to be 98.6% as analyzed by NMR spectroscopy. Chemical composition of the final biodiesel was also determined by GC-MS analysis. PMID:24987726

Amperometric glucose biosensor with remarkable acid stability based on glucose oxidase entrapped in colloidal gold-modified carbon ionic liquid electrode.

PubMed

Liu, Xiaoying; Zeng, Xiandong; Mai, Nannan; Liu, Yong; Kong, Bo; Li, Yonghong; Wei, Wanzhi; Luo, Shenglian

2010-08-15

A colloidal gold-modified carbon ionic liquid electrode was constructed by mixing colloidal gold-modified graphite powder with a solid room temperature ionic liquid n-octyl-pyridinium hexafluorophosphate (OPPF(6)). Glucose oxidase (GOD) was entrapped in this composite matrix and maintained its bioactivity well and displayed excellent stability. The effect conditions of pH, applied potential and GOD loading were examined. Especially, the glucose oxidase entrapped in this carbon ionic liquid electrode fully retained its activity upon stressing in strongly acidic conditions (pH 2.0) for over one hour. The proposed biosensor responds to glucose linearly over concentration range of 5.0x10(-6) to 1.2x10(-3) and 2.6x10(-3) to 1.3x10(-2) M, and the detection limit is 3.5x10(-6) M. The response time of the biosensor is fast (within 10s), and the life time is over two months. The effects of electroactive interferents, such as ascorbic acid, uric acid, can be significantly reduced by a Nafion film casting on the surface of resulting biosensor. Copyright 2010 Elsevier B.V. All rights reserved.

Useful halophilic, thermostable and ionic liquids tolerant cellulases

DOEpatents

Zhang, Tao; Datta, Supratim; Simmons, Blake A.; Rubin, Edward M.

2016-06-28

The present invention provides for an isolated or recombinant polypeptide comprising an amino acid sequence having at least 70% identity with the amino acid sequence of a Halorhabdus utahensis cellulase, such as Hu-CBH1, wherein said amino acid sequence has a halophilic thermostable and/or thermophilic cellobiohydrolase (CBH) activity. In some embodiments, the polypeptide has a CBH activity that is resistant to up to about 20% of ionic liquids. The present invention also provides for compositions comprising and methods using the isolated or recombinant polypeptide.

A Flemion-based actuator with ionic liquid as solvent

NASA Astrophysics Data System (ADS)

Wang, Jin; Xu, Chunye; Taya, Minoru; Kuga, Yasuo

2007-04-01

A perfluorinated carboxylic acid membrane, i.e. Flemion, shows improved performance as actuator material compared with Nafion (perfluorinated sulfonic acid). Flemion has a higher ion exchange capacity and good mechanical strength. In particular, Flemion will deform with no back relaxation under applied electrical stimulus. However, with water as solvent, the operation of Flemion in air has serious problems, since water would evaporate quickly in air. Moreover, the electrochemical stability for use in water is around 1 V at room temperature. In previous work, investigations on Nafion with ionic liquid as solvents have been carried out by some researchers and good results have been obtained. In this work, we explore the use of highly stable ionic liquid instead of water as solvent in Flemion. Experimental results indicate that Flemion-based actuators with ionic liquid as solvent have improved stability as compared to the water samples. Although the forces exhibited by Flemion-based actuators with the use of ionic liquid decreased dramatically compared to water, these preliminary results suggest good potential for the use of Flemion with ionic liquid in future applications.

Flemion-based actuator with ionic liquid as solvent

NASA Astrophysics Data System (ADS)

Wang, Jin; Xu, Chunye; Taya, Minoru; Kuga, Yasuo

2006-03-01

A perfluorinated carboxylic acid membrane, i.e. Flemion, shows improved performance as actuator material compared with Nafion (perfluorinated sulfonic acide). Flemion has a higher ion exchange capacity and good mechanical strength. Especially, Flemion will deform with no back relaxation when applied electrical stimulus. However, with water as solvent, the operation of Flemion in air has serious problems. Since water would evaporate quickly in air. Moreover, the electrochemical stability for use in water is around 1V at room temperature. In previous work, investigations on Nafion with ionic liquid as solvents have been carried out and good results have been obtained. In this work, we explore the use of highly stable ionic liquid instead of water as solvent in Flemion. Experimental results indicate that Flemion based actuators with ionic liquid as solvent have improved stability as compared to the water samples. Although the forces exhibited by Flemion based actuators with the use of ionic liquid decreased dramatically as compared to water, these preliminary results suggest a good potential for use of Flemion with ionic liquid in some applications.

Global transcriptome response to ionic liquid by a tropical rain forest soil bacterium, Enterobacter lignolyticus.

PubMed

Khudyakov, Jane I; D'haeseleer, Patrik; Borglin, Sharon E; Deangelis, Kristen M; Woo, Hannah; Lindquist, Erika A; Hazen, Terry C; Simmons, Blake A; Thelen, Michael P

2012-08-07

To process plant-based renewable biofuels, pretreatment of plant feedstock with ionic liquids has significant advantages over current methods for deconstruction of lignocellulosic feedstocks. However, ionic liquids are often toxic to the microorganisms used subsequently for biomass saccharification and fermentation. We previously isolated Enterobacter lignolyticus strain SCF1, a lignocellulolytic bacterium from tropical rain forest soil, and report here that it can grow in the presence of 0.5 M 1-ethyl-3-methylimidazolium chloride, a commonly used ionic liquid. We investigated molecular mechanisms of SCF1 ionic liquid tolerance using a combination of phenotypic growth assays, phospholipid fatty acid analysis, and RNA sequencing technologies. Potential modes of resistance to 1-ethyl-3-methylimidazolium chloride include an increase in cyclopropane fatty acids in the cell membrane, scavenging of compatible solutes, up-regulation of osmoprotectant transporters and drug efflux pumps, and down-regulation of membrane porins. These findings represent an important first step in understanding mechanisms of ionic liquid resistance in bacteria and provide a basis for engineering microbial tolerance.

Liquid-liquid extraction of neodymium(III) by dialkylphosphate ionic liquids from acidic medium: the importance of the ionic liquid cation.

PubMed

Rout, Alok; Kotlarska, Justyna; Dehaen, Wim; Binnemans, Koen

2013-10-21

The ionic liquids 1-hexyl-3-methylimidazolium bis(2-ethylhexyl)phosphate, [C6mim][DEHP], 1-hexyl-1-methylpyrrolidinium bis(2-ethylhexyl)phosphate, [C6mpyr][DEHP], and tetrabutylammonium bis(2-ethylhexyl)phosphate, [N4444][DEHP], were prepared and characterized using (1)H and (13)C NMR spectroscopy. The extraction behavior of neodymium(iii) from nitrate medium by these ionic liquids, diluted with the room temperature ionic liquids 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C6mim][NTf2], 1-hexyl-3-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, [C6mpyr][NTf2], and tributylmethylammonium bis(trifluoromethylsulfonyl)imide, [N1444][NTf2], was studied. The distribution ratio of neodymium(iii) was measured as a function of various parameters, such as pH, concentration of the ionic liquid extractant, nature of diluents, concentration of ionic liquid cations and nitrate anions in the aqueous phase. The extraction behavior was compared with that obtained for a solution of the molecular extractant bis(2-ethylhexyl)phosphoric acid (DEHPA) in an ionic liquid diluent. The extraction of neodymium(iii) in the ionic liquids [C6mim][DEHP] and [C6mpyr][DEHP] showed markedly different extraction properties in comparison with that of the quaternary ammonium analogue [N4444][DEHP], especially concerning the pH dependence of the extraction process. These results show that the extraction process can be tuned by the selection of the ionic liquid cation. The extraction experiments also included the trivalent rare-earth ions lanthanum(iii), cerium(iii), praseodymium(iii), ytterbium(iii) and yttrium(iii). Studies of the stripping behavior and the reusability of the ionic liquids were carried out, which indicate that the ionic liquids can be reused with no loss in activity.

Solvent extraction separation of Th-227 and Ac-225 in room temperature ionic liquids

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

Bell, Jason R; Boll, Rose Ann; Dai, Sheng

2012-01-01

The solvent extractions of Th-227 and Ac-225 from the aqueous phase into ionic liquids (ILs) were investigated by using N,N,N ,N - tetraoctyldiglycolamide (TODGA) or di(2-ethylhexyl)phosphoric acid (HDEHP) as an extractant. Four ionic liquids, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C4mim][NTf2]), 1-butyl-3-methylimidazolium bis(perfluoroethanesulfonyl)imide ([C4mim][BETI]), 1-butyl-2,3-trimethyleneimidazolium (trifluoromethanesulfonyl)imide [BuI5][NTf2], and 1-benzyl pyridinium bis(trifluoromethanesulfonyl)imide ([PhCH2Py][NTf2]) were used as extraction solvents for separation of Th-227 and Ac-225 in this study. Excellent extraction efficiencies and selectivities were found for Th-227/Ac-225 when HDEHP was used as an extractant in these ionic liquids. The effects of different extractant concentrations in ionic liquids and acidities of the aqueous phase on extraction efficienciesmore » and selectivities of Th-227/Ac-225 are also presented in this article.« less

Advances in the analysis of biological samples using ionic liquids.

PubMed

Clark, Kevin D; Trujillo-Rodríguez, María J; Anderson, Jared L

2018-02-12

Ionic liquids are a class of solvents and materials that hold great promise in bioanalytical chemistry. Task-specific ionic liquids have recently been designed for the selective extraction, separation, and detection of proteins, peptides, nucleic acids, and other physiologically relevant analytes from complex biological samples. To facilitate rapid bioanalysis, ionic liquids have been integrated in miniaturized and automated procedures. Bioanalytical separations have also benefited from the modification of nonspecific magnetic materials with ionic liquids or the implementation of ionic liquids with inherent magnetic properties. Furthermore, the direct detection of the extracted molecules in the analytical instrument has been demonstrated with structurally tuned ionic liquids and magnetic ionic liquids, providing a significant advantage in the analysis of low-abundance analytes. This article gives an overview of these advances that involve the application of ionic liquids and derivatives in bioanalysis. Graphical abstract Ionic liquids, magnetic ionic liquids, and ionic liquid-based sorbents are increasing the speed, selectivity, and sensitivity in the analysis of biological samples.

Indirect ultraviolet detection of alkaline earth metal ions using an imidazolium ionic liquid as an ultraviolet absorption reagent in ion chromatography.

PubMed

Liu, Yong-Qiang; Yu, Hong

2017-04-01

A convenient and versatile method was developed for the separation and detection of alkaline earth metal ions by ion chromatography with indirect UV detection. The chromatographic separation of Mg 2+ , Ca 2+ , and Sr 2+ was performed on a carboxylic acid base cation exchange column using imidazolium ionic liquid/acid as the mobile phase, in which the imidazolium ionic liquid acted as an UV-absorption reagent. The effects of imidazolium ionic liquids, detection wavelength, acids in the mobile phase, and column temperature on the retention of Mg 2+ , Ca 2+ , and Sr 2+ were investigated. The main factors influencing the separation and detection were the background UV absorption reagent and the concentration of hydrogen ion in ion chromatography with indirect UV detection. The successful separation and detection of Mg 2+ , Ca 2+ , and Sr 2+ within 14 min were achieved using the selected chromatographic conditions, and the detection limits (S/N = 3) were 0.06, 0.12, and 0.23 mg/L, respectively. A new separation and detection method of alkaline earth metal ions by ion chromatography with indirect UV detection was developed, and the application range of ionic liquids was expanded. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Physical Properties of Substituted Imidazolium Based Ionic Liquids Gel Electrolytes

NASA Astrophysics Data System (ADS)

Sutto, Thomas E.; De Long, Hugh C.; Trulove, Paul C.

2002-11-01

The physical properties of solid gel electrolytes of either polyvinylidene diflurohexafluoropropylene or a combination of polyvinylidene hexafluoropropylene and polyacrylic acid, and the molten salts 1-ethyl-3-methylimidazolium tetrafluoroborate, 1,2-dimethyl-3-n-propylimidazolium tetrafluoroborate, and the new molten salts 1,2-dimethyl-3-n-butylimidazolium tetrafluoroborate, and 1,2-dimethyl-3-n-butylimidazolium hexafluorophosphate were characterized by temperature dependent ionic conductivity measurements for both the pure molten salt and of the molten salt with 0.5 M Li+ present. Ionic conductivity data indicate that for each of the molten salts, the highest concentration of molten salt allowable in a single component polymer gel was 85%, while gels composed of 90%molten salt were possible when using both polyvinylidene hexafluorophosphate and polyacrylic acid. For polymer gel composites prepared using lithium containing ionic liquids, the optimum polymer gel composite consisted of 85% of the 0.5 M Li+/ionic liquid, 12.75% polyvinylidene hexafluoropropylene, and 2.25% poly (1-carboxyethylene). The highest ionic conductivity observed was for the gel containing 90%1-ethyl-3-methyl-imidazolium tetrafluoroborate, 9.08 mS/cm. For the lithium containing ionic liquid gels, their ionic conductivity ranged from 1.45 to 0.05 mS/cm, which is comparable to the value of 0.91 mS/cm, observed for polymer composite gels containing 0.5 M LiBF4 in propylene carbonate.

Hollow porous ionic liquids composite polymers based solid phase extraction coupled online with high performance liquid chromatography for selective analysis of hydrophilic hydroxybenzoic acids from complex samples.

PubMed

Dai, Xingping; Wang, Dongsheng; Li, Hui; Chen, Yanyi; Gong, Zhicheng; Xiang, Haiyan; Shi, Shuyun; Chen, Xiaoqing

2017-02-10

Polar and hydrophilic properties of hydroxybenzoic acids usually made them coelute with interferences in high performance liquid chromatography (HPLC) analysis. Then selective analysis of them was necessary. Herein, hollow porous ionic liquids composite polymers (PILs) based solid phase extraction (SPE) was firstly fabricated and coupled online with HPLC for selective analysis of hydroxybenzoic acids from complex matrices. Hollow porous PILs were firstly synthesized using Mobil Composition of Matter No. 48 (MCM-48) spheres as sacrificial support, 1-vinyl-3-methylimidazolium chloride (VMIM + Cl - ) as monomer, and ethylene glycol dimethacrylate (EGDMA) as cross-linker. Various parameters affecting synthesis, adsorption and desorption behaviors were investigated and optimized. Steady-state adsorption studies showed the resulting hollow porous PILs exhibited high adsorption capacity, fast adsorption kinetics, and excellent specific adsorption. Subsequently, the application of online SPE system was studied by selective analysis of protocatechuic acid (PCA), 4-hydroxybenzoic acid (4-HBA), and vanillic acid (VA) from Pollen Typha angustifolia. The obtained limit of detection (LOD) varied from 0.002 to 0.01μg/mL, the linear range (0.05-5.0μg/mL) was wide with correlation coefficient (R) from 0.9982 to 0.9994, and the average recoveries at three spiking levels ranged from 82.7 to 102.4%, with column-to-column relative standard deviation (RSD) below 8.1%. The proposed online method showed good accuracy, precision, specificity and convenience, which opened up a universal and efficient route for selective analysis of hydroxybenzoic acids from complex samples. Copyright © 2017 Elsevier B.V. All rights reserved.

Evaluation of Adsorption Characteristics of a Fibrous Adsorbent Containing Zwitter-Ionic Functional Group, Targeting Organic Acids.

PubMed

Nakazawa, Akira; Tang, Ning; Inoue, Yoshinori; Kamichatani, Waka; Katoh, Toshifumi; Saito, Mitsuru; Obara, Kenji; Toriba, Akira; Hayakawa, Kazuichi

2017-01-01

Diallylamine-maleic acid copolymer (DAM)-nonwoven fabric (DAM-f), a fibrous adsorbent, contains DAM with zwitter-ionic functional groups and forms a hydration layer on the surface. The aim of this report was to evaluate the adsorption selectivity of DAM-f to semi-volatile organic acid (C1-C5). In the aqueous phase, formic acid dissolved in the hydration layer bound to the imino group of DAM-f due to anion exchange interaction. In the gas phase, the adsorption amounts of organic acids increased with the exposure time. Moreover, the adsorption rate constants correlated with the air/water partition coefficients (log K aw ) for formic acid, propionic acid, butyric acid, valeric acid and isovaleric acid, except for acetic acid. These results indicate that DAM-f is highly selective to hydrophilic compounds which easily move from the air to the hydration layer of DAM-f.

Temperature regulated Brønsted acidic ionic liquid-catalyze esterification of oleic acid for biodiesel application

NASA Astrophysics Data System (ADS)

Rafiee, Ezzat; Mirnezami, Fakhrosadat

2017-02-01

By combining phosphotungstic acid (PW) and SO3H- functioned zwitterion, heteropoly anion-based Brønsted acidic ionic liquids (HPA-ILs) were successfully obtained. Scanning electron microscopy and energy dispersive X-ray spectroscopy were provided the morphology and composition of the prepared material. Catalytic performance and reusability of the catalysts were evaluated through an esterification reaction between oleic acid and methanol for production of biodiesel. Relationship between catalytic activities and acidity of the catalysts have been discussed by potentiometric titration. The results showed that HPA-ILs had good activity and reusability. HPA-ILs dissolved in the reaction mixture during the reaction process and could be precipitated and separated from products at lower temperature.

Sequencing proteins with transverse ionic transport in nanochannels.

PubMed

Boynton, Paul; Di Ventra, Massimiliano

2016-05-03

De novo protein sequencing is essential for understanding cellular processes that govern the function of living organisms and all sequence modifications that occur after a protein has been constructed from its corresponding DNA code. By obtaining the order of the amino acids that compose a given protein one can then determine both its secondary and tertiary structures through structure prediction, which is used to create models for protein aggregation diseases such as Alzheimer's Disease. Here, we propose a new technique for de novo protein sequencing that involves translocating a polypeptide through a synthetic nanochannel and measuring the ionic current of each amino acid through an intersecting perpendicular nanochannel. We find that the distribution of ionic currents for each of the 20 proteinogenic amino acids encoded by eukaryotic genes is statistically distinct, showing this technique's potential for de novo protein sequencing.

Methods of hydrolyzing a cellulose using halophilic, thermostable and ionic liquids tolerant cellulases

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

Zhang, Tao; Datta, Supratim; Simmons, Blake A.

The present invention provides for an isolated or recombinant polypeptide comprising an amino acid sequence having at least 70% identity with the amino acid sequence of a Halorhabdus utahensis cellulase, such as Hu-CBH1, wherein said amino acid sequence has a halophilic thermostable and/or thermophilic cellobiohydrolase (CBH) activity. In some embodiments, the polypeptide has a CBH activity that is resistant to up to about 20% of ionic liquids. The present invention also provides for compositions comprising and methods using the isolated or recombinant polypeptide.

Evaluation of factors influencing the enantioselective enzymatic esterification of lactic acid in ionic liquid.

PubMed

Findrik, Zvjezdana; Németh, Gergely; Gubicza, László; Bélafi-Bakó, Katalin; Vasić-Rački, Durđa

2012-05-01

In this paper esterification of ethanol and lactic acid catalyzed by Candida antarctica B (Novozyme 435) in ionic liquid (Cyphos 104) was studied. The influence of different variables on lipase enantioselectivity and lactic acid conversion was investigated. The variables investigated were ionic liquid mass/lipase mass ratio, water content, alcohol excess and temperature. Using the Design Expert software 2(3) factorial experimental plan (two levels, three factors) was performed to ascertain the effect of selected variables and their interactions on the ethyl lactate enantiomeric excess and lactic acid conversion. The results of the experiments and statistical processing suggest that temperature and alcohol excess have the highest effect on the ethyl lactate enantiomeric excess, while temperature and water content have the highest influence on the lactic acid conversion. The statistical mathematical model developed on the basis of the experimental data showed that the highest enantiomeric excess achieved in the investigated variable range is 34.3%, and the highest conversion is 63.8% at the initial conditions of water content at 8%; 11-fold molar excess of alcohol and temperature at 30 °C.

Anisotropic amplification of proton transport in proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Thimmappa, Ravikumar; Fawaz, Mohammed; Devendrachari, Mruthyunjayachari Chattanahalli; Gautam, Manu; Kottaichamy, Alagar Raja; Shafi, Shahid Pottachola; Thotiyl, Musthafa Ottakam

2017-07-01

Though graphene oxide (GO) membrane shuttles protons under humid conditions, it suffer severe disintegration and anhydrous conditions lead to abysmal ionic conductivity. The trade-off between mechanical integrity and ionic conductivity challenge the amplification of GO's ionic transport under anhydrous conditions. We show anisotropic amplification of GO's ionic transport with a selective amplification of in plane contribution under anhydrous conditions by doping it with a plant extract, phytic acid (PA). The hygroscopic nature of PA stabilized interlayer water molecules and peculiar geometry of sbnd OH functionalities around saturated hydrocarbon ring anisotropically enhanced ionic transport amplifying the fuel cell performance metrics.

A Simplified Undergraduate Laboratory Experiment to Evaluate the Effect of the Ionic Strength on the Equilibrium Concentration Quotient of the Bromcresol Green Dye

ERIC Educational Resources Information Center

Rodriguez, Hernan B.; Mirenda, Martin

2012-01-01

A modified laboratory experiment for undergraduate students is presented to evaluate the effects of the ionic strength, "I", on the equilibrium concentration quotient, K[subscript c], of the acid-base indicator bromcresol green (BCG). The two-step deprotonation of the acidic form of the dye (sultone form), as it is dissolved in water, yields…

Selective extraction and recovery of rare earth metals from phosphor powders in waste fluorescent lamps using an ionic liquid system.

PubMed

Yang, Fan; Kubota, Fukiko; Baba, Yuzo; Kamiya, Noriho; Goto, Masahiro

2013-06-15

The recycling of rare earth metals from phosphor powders in waste fluorescent lamps by solvent extraction using ionic liquids was studied. Acid leaching of rare earth metals from the waste phosphor powder was examined first. Yttrium (Y) and europium (Eu) dissolved readily in the acid solution; however, the leaching of other rare earth metals required substantial energy input. Ionization of target rare earth metals from the waste phosphor powders into the leach solution was critical for their successful recovery. As a high temperature was required for the complete leaching of all rare earth metals, ionic liquids, for which vapor pressure is negligible, were used as an alternative extracting phase to the conventional organic diluent. An extractant, N, N-dioctyldiglycol amic acid (DODGAA), which was recently developed, showed a high affinity for rare earth metal ions in liquid-liquid extraction although a conventional commercial phosphonic extractant did not. An effective recovery of the rare earth metals, Y, Eu, La and Ce, from the metal impurities, Fe, Al and Zn, was achieved from the acidic leach solution of phosphor powders using an ionic liquid containing DODGAA as novel extractant system. Copyright © 2013 Elsevier B.V. All rights reserved.

Failure Mechanisms of Hollow Fiber Supported Ionic Liquid Membranes

PubMed Central

Zeh, Matthew; Wickramanayake, Shan; Hopkinson, David

2016-01-01

Hollow fiber supported ionic liquid membranes (SILMs) were tested using the bubble point method to investigate potential failure modes, including the maximum transmembrane pressure before loss of the ionic liquid from the support. Porous hollow fiber supports were fabricated with different pore morphologies using Matrimid® and Torlon® as the polymeric material and 1-hexyl-3-methylimidalzolium bis(trifluoromethylsulfonyl)imide ([C6mim][Tf2N]) as the ionic liquid (IL) component. Hollow fiber SILMs were tested for their maximum pressure before failure, with pressure applied either from the bore side or shell side. It was found that the membranes exhibited one or more of three different modes of failure when pressurized: liquid loss (occurring at the bubble point), rupture, and collapse. PMID:27023620

Immobilization of molecular catalysts in supported ionic liquid phases.

PubMed

Van Doorslaer, Charlie; Wahlen, Joos; Mertens, Pascal; Binnemans, Koen; De Vos, Dirk

2010-09-28

In a supported ionic liquid phase (SILP) catalyst system, an ionic liquid (IL) film is immobilized on a high-surface area porous solid and a homogeneous catalyst is dissolved in this supported IL layer, thereby combining the attractive features of homogeneous catalysts with the benefits of heterogeneous catalysts. In this review reliable strategies for the immobilization of molecular catalysts in SILPs are surveyed. In the first part, general aspects concerning the application of SILP catalysts are presented, focusing on the type of catalyst, support, ionic liquid and reaction conditions. Secondly, organic reactions in which SILP technology is applied to improve the performance of homogeneous transition-metal catalysts are presented: hydroformylation, metathesis reactions, carbonylation, hydrogenation, hydroamination, coupling reactions and asymmetric reactions.

Furfural production in biphasic media using an acidic ionic liquid as a catalyst.

PubMed

Peleteiro, Susana; Santos, Valentín; Parajó, Juan C

2016-11-20

Ionic liquids are valuable tools for biorefineries. This study provides an experimental assessment on the utilization of an acidic ionic liquid (1-butyl-3-methylimidazolium hydrogen sulfate) as a catalyst for furfural production in water/solvent media. The substrates employed in experiments were commercial xylose (employed as a reference compound) or hemicellulosic saccharides obtained by hydrothermal processing of Eucalyptus globulus wood (which were employed as produced, after membrane concentration or after freeze-drying). A variety of reaction conditions (defined by temperature, reaction time and type of organic solvent) were considered. The possibility of recycling the catalyst was assessed in selected experiments. Copyright © 2016 Elsevier Ltd. All rights reserved.

Thermophysical properties of tri-n-butylphosphate-ionic liquid mixture

NASA Astrophysics Data System (ADS)

Rout, Alok; Mishra, Satyabrata; Venkatesan, K. A.; Antony, M. P.; Pandey, N. K.

2018-04-01

Thermophysical properties such as viscosity, density, energy of activation and coefficient of thermal expansion were measured for the solvent phase composed of tri-n-butylphosphate (TBP), 1-butyl-3-methylimidazolium bis(trifluoromethane-sulfonyl)imide ([C4mim][NTf2]) and 1.1 M TBP/[C4mim][NTf2]. The results were compared with that of nitric acid equilibrated [C4mim][NTf2] and 1.1M TBP/[C4mim][NTf2]. Thermal stability of the ionic liquid phase was assessed by using differential scanning calorimetric (DSC) technique. Other important physical properties such as refractive index and surface tension of the ionic liquid phase composition were evaluated before and after acid saturation.

High conductive, long-term durable, anhydrous proton conductive solid-state electrolyte based on a metal-organic framework impregnated with binary ionic liquids: Synthesis, characteristic and effect of anion

NASA Astrophysics Data System (ADS)

Chen, Hui; Han, Shu-Yan; Liu, Rui-Heng; Chen, Teng-Fei; Bi, Kai-Lun; Liang, Jian-Bo; Deng, Yu-Heng; Wan, Chong-Qing

2018-02-01

Incorporating ionic liquids (abbreviated as ILs) into porous metal-organic framework (MOF) to obtain ILs@MOF nanocomposites is documented as a feasible method to achieve new type of anhydrous proton conductor with high performance. We newly synthesized a series of ILs with different acid counter anions (R-SO3-) and their ILs@MOF hybrid materials, i.e. SA-EIMS@MIL-101, MSA-EIMS@MIL-101 and PTSA-EIMS@MIL-101 (SA = sulfate acid, MSA = methanesulfonate acid, PTSA = p-toluenesulfonate acid, EIMS = 1-(1-ethyl-3-imidazolium)propane-3-sulfonate). Such hybrid materials displayed as anhydrous proton conduction with long-term durability even heated at 150 °C open to air. σ value of SA-EIMS@MIL-101 is up to 1.89 × 10-3 S cm-1, being in the range of the most conductive MOF-based materials. MOF support exhibited favorable proton transport and long-term retention for ILs. Anion volumes of R-SO3- displayed significant effects on the proton conductivity of such hybrid ILs@MOF materials. The smaller the van der Waals volume of R-SO3- is, the higher the conductivity of ILs@MOF is. This work suggests that the combination of a variety of the incorporated ILs and a MOF framework would afford high proton transport and gives an idea to explore the safe, anhydrous, solid-state electrolyte for high temperature proton exchange membrane fuel cell.

Oxidative desulfurization of dibenzothiophene from model oil using ionic liquids as extracting agent

NASA Astrophysics Data System (ADS)

Taha, Mohd F.; Atikah, N.; Chong, F. K.; Shaharun, Maizatul S.

2012-09-01

The oxidative desulfurization of dibenzothiophene (DBT) from model oil (in n-dodecane) was carried out using ionic liquid as the extractant and catalyst, and hydrogen peroxide (H2O2) in combination with acetic acid (CH3COOH) and sulphuric acid (H2SO4) as the oxidant. The ionic liquids used were 1-butyl-3-methylimidazolium octyl sulphate ([Bmim][OcSO4]) and 1-butyl-3-methylimidazolium acetate ([Bmim][Ac]). The effect of the amounts of H2O2 on oxidative desulphurization of model oil was first investigated without the usage of ionic liquids at room temperature. The results indicate that greater amount of H2O2 give higher desulfurization and the maximum desulfurization in this study, i.e. 34 %, was occurred when the molar ratio of H2O2 to sulfur was 5:1. With the usage of ionic liquid and the molar ratio of 5:1 (H2O2:sulfur), the efficiency of DBT removal from model oil was increased significantly in terms of percent removal and removal time. Ionic liquid of [Bmim][OcSO4] performed better than [Bmim][Ac] with 72 % DBT removal. When molar ratio of H2O2 to sulphur was 5:1, volume ratio of ionic liquid to model oil was 1:1 and mixing time was 60 min at room temperature. The results indicate the potential of ionic liquids as the extractant and catalyst for oxidative desulfurization of hydrocarbon fuels.

Interaction of copper and fulvic acid at the hematite-water interface

NASA Astrophysics Data System (ADS)

Christl, Iso; Kretzschmar, Ruben

2001-10-01

The influence of surface-bound fulvic acid on the sorption of Cu(II) to colloidal hematite particles was studied experimentally and the results were compared with model calculations based on the linear additivity assumption. In the first step, proton and Cu binding to colloidal hematite particles and to purified fulvic acid was studied by batch equilibration and ion-selective electrode titration experiments, respectively. The sorption data for these binary systems were modeled with a basic Stern surface complexation model for hematite and the NICA-Donnan model for fulvic acid. In the second step, pH-dependent sorption of Cu and fulvic acid in ternary systems containing Cu, hematite, and fulvic acid in NaNO3 electrolyte solutions was investigated in batch sorption experiments. Sorption of fulvic acid to the hematite decreased with increasing pH (pH 3-10) and decreasing ionic strength (0.01-0.1 M NaNO3), while the presence of 22 μM Cu had a small effect on fulvic acid sorption, only detectable at low ionic strength (0.01 M). Sorption of Cu to the solid phase separated by centrifugation was strongly affected by the presence of fulvic acid. Below pH 6, sorption of Cu to the solid phase increased by up to 40% compared with the pure hematite. Above pH 6, the presence of fulvic acid resulted in a decrease in Cu sorption due to increasing concentrations of dissolved metal-organic complexes. At low ionic strength (0.01 M), the effects of fulvic acid on Cu sorption to the solid phase were more pronounced than at higher ionic strength (0.1 M). Comparison of the experimental data with model calculations shows that Cu sorption in ternary hematite-fulvic acid systems is systematically underestimated by up to 30% using the linear additivity assumption. Therefore, specific interactions between organic matter and trace metal cations at mineral surfaces must be taken into account when applying surface complexation models to soils or sediments which contain oxides and natural organic matter.

Transport and deposition of Suwannee River Humic Acid/Natural Organic Matter formed silver nanoparticles on silica matrices: the influence of solution pH and ionic strength.

PubMed

Akaighe, Nelson; Depner, Sean W; Banerjee, Sarbajit; Sohn, Mary

2013-07-01

The transport and deposition of silver nanoparticles (AgNPs) formed from Ag(+) reduction by Suwannee River Humic Acid (SRHA) and Suwannee River Natural Organic Matter (SRNOM) utilizing a silica matrix is reported. The morphology and stability of the AgNPs was analyzed by transmission electron microscopy (TEM), dynamic light scattering (DLS) and zeta potential measurements. The percentage conversion of the initial [Ag(+)] to [AgNPs] was determined from a combination of atomic absorption (AAS) and UV-Vis spectroscopy, and centrifugation techniques. The results indicate higher AgNP transport and consequently low deposition in the porous media at basic pH conditions and low ionic strength. However, at low acidic pH and high ionic strength, especially with the divalent metallic cations, the mobility of the AgNPs in the porous media was very low, most likely due to NP aggregation. Overall, the results suggest the potential for AgNP contamination of subsurface soils and groundwater aquifers is mostly dependent on their aggregation state, controlled by the soil water and sediment ionic strength and pH. Copyright © 2013 Elsevier Ltd. All rights reserved.

Chiral separation of phenylalanine and tryptophan by capillary electrophoresis using a mixture of β-CD and chiral ionic liquid ([TBA] [L-ASP]) as selectors.

PubMed

Yujiao, Wu; Guoyan, Wang; Wenyan, Zhao; Hongfen, Zhang; Huanwang, Jing; Anjia, Chen

2014-05-01

In this paper, a simple, effective and green capillary electrophoresis separation and detection method was developed for the quantification of underivatized amino acids (dl-phenylalanine; dl-tryptophan) using β-Cyclodextrin and chiral ionic liquid ([TBA] [l-ASP]) as selectors. Separation parameters such as buffer concentrations, pH, β-CD and chiral ionic liquid concentrations and separation voltage were investigated for the enantioseparation in order to achieve the maximum possible resolution. A good separation was achieved in a background electrolyte composed of 15 mm sodium tetraborate, 5 mm β-CD and 4 mm chiral ionic liquid at pH 9.5, and an applied voltage of 10 kV. Under optimum conditions, linearity was achieved within concentration ranges from 0.08 to 10 µg/mL for the analytes with correlation coefficients from 0.9956 to 0.9998, and the analytes were separated in less than 6 min with efficiencies up to 970,000 plates/m. The proposed method was successfully applied to the determination of amino acid enantiomers in compound amino acids injections, such as 18AA-I, 18AA-II and 3AA.

Alkaline ionic liquids applied in supported ionic liquid catalyst for selective hydrogenation of citral to citronellal

PubMed Central

Salminen, Eero; Virtanen, Pasi; Mikkola, Jyri-Pekka

2014-01-01

The challenge in preparation of ionic liquids containing a strong alkaline anion is to identify a suitable cation which can tolerate the harsh conditions induced by the anion. In this study, a commercial quaternary ammonium compound (quat) benzalkonium [ADBA] (alkyldimethylbenzylammonium) was used as a cation in the synthesis of different alkaline ionic liquids. In fact, the precursor, benzalkonium chloride, is a mixture of alkyldimethylbenzylammonium chlorides of various alkyl chain lengths and is commonly used in the formulation of various antiseptic products. The prepared ionic liquids were utilized as Supported Ionic Liquid Catalysts (SILCAs). Typically, a SILCA contains metal nanoparticles, enzymes, or metal complexes in an ionic liquid layer which is immobilized on a solid carrier material such as an active carbon cloth (ACC). The catalysts were applied in the selective hydrogenation of citral to citronellal which is an important perfumery chemical. Interestingly, 70% molar yield toward citronellal was achieved over a catalyst containing the alkaline ionic liquid benzalkonium methoxide. PMID:24790972

Ionic liquids as a reaction medium for lipase-catalyzed methanolysis of sunflower oil.

PubMed

Sunitha, S; Kanjilal, S; Reddy, P S; Prasad, R B N

2007-12-01

Ionic liquids, 1-butyl-3-methyl imidazolium hexafluorophosphate ([BMIm][PF(6)]) and 1-ethyl-3-methyl imidazolium hexafluorophosphate ([EMIm][PF(6)]), were used for the methanolysis of sunflower oil using Candida antarctica lipase (Novozyme 435) and gave yields of fatty acid methyl esters at 98-99% within 10 h. The optimum conditions of methanolysis in hydrophobic ionic liquids are 2% (w/w) lipase, 1:1 (w/w) oil/ionic liquid and 1:8 (mol/mol) oil/methanol at 58-60 degrees C. Methanolysis using hydrophilic ionic liquids, 3-methyl imidazolium tetrafluoroborate ([HMIm][BF(4)]) and 1-butyl-3-methyl imidazolium tetrafluoroborate ([BMIm][BF(4)]), gave very poor yields. A hydrophobic ionic liquid thus protects the lipase from methanol. Recovered ionic liquids and lipase were used for four successive reaction cycles without any significant loss of activity.

Symposium: Ionic and Respiratory Interaction in Aquatic Animals

ERIC Educational Resources Information Center

Physiologist, 1976

1976-01-01

Presented are eight abstracts of a symposium held in conjunction with the American Physiological Society (APS) and the American Society of Zoologists (ASZ). Fish gill structure and function, renal function, acid-base balance and ionic sensitivity are topics discussed. (EB)

Highly water-dispersible, mixed ionic-electronic conducting, polymer acid-doped polyanilines as ionomers for direct methanol fuel cells.

PubMed

Murthy, Arun; Manthiram, Arumugam

2011-06-28

Highly water-dispersible polymer acid-doped polyanilines have been synthesized and evaluated as an alternative for expensive Nafion ionomers in the anode of direct methanol fuel cells (DMFC). These polymers as ionomers lead to higher performance in single cell DMFC compared to Nafion ionomers due to mixed ionic-electronic conduction, water dispersibility, and co-catalytic activity. This journal is © The Royal Society of Chemistry 2011

Methods for conversion of carbohydrates in ionic liquids to value-added chemicals

DOEpatents

Zhao, Haibo [The Woodlands, TX; Holladay, Johnathan E [Kennewick, WA; Zhang, Zongchao C [Norwood, NJ

2011-05-10

Methods are described for converting carbohydrates including, e.g., monosaccharides, disaccharides, and polysaccharides in ionic liquids to value-added chemicals including furans, useful as chemical intermediates and/or feedstocks. Fructose is converted to 5-hydroxylmethylfurfural (HMF) in the presence of metal halide and acid catalysts. Glucose is effectively converted to HMF in the presence of chromium chloride catalysts. Yields of up to about 70% are achieved with low levels of impurities such as levulinic acid.

Catalytic conversion of cellulose to fuels and chemicals using boronic acids

DOEpatents

Raines, Ronald; Caes, Benjamin; Palte, Michael

2015-10-20

Methods and catalyst compositions for formation of furans from carbohydrates. A carbohydrate substrate is heating in the presence of a 2-substituted phenylboronic acid (or salt or hydrate thereof) and optionally a magnesium or calcium halide salt. The reaction is carried out in a polar aprotic solvent other than an ionic liquid, an ionic liquid or a mixture thereof. Additional of a selected amount of water to the reaction can enhance the yield of furans.

Development of Monopole Interaction Models for Ionic Compounds. Part I: Estimation of Aqueous Henry's Law Constants for Ions and Gas Phase pKa Values for Acidic Compounds.

PubMed

Hilal, S H; Saravanaraj, A N; Carreira, L A

2014-02-01

The SPARC (SPARC Performs Automated Reasoning in Chemistry) physicochemical mechanistic models for neutral compounds have been extended to estimate Henry's Law Constant (HLC) for charged species by incorporating ionic electrostatic interaction models. Combinations of absolute aqueous pKa values, relative pKa values in the gas phase, and aqueous HLC for neutral compounds have been used to develop monopole interaction models that quantify the energy differences upon moving an ionic solute molecule from the gas phase to the liquid phase. Inter-molecular interaction energies were factored into mechanistic contributions of monopoles with polarizability, dipole, H-bonding, and resonance. The monopole ionic models were validated by a wide range of measured gas phase pKa data for 450 acidic compounds. The RMS deviation error and R(2) for the OH, SH, CO2 H, CH3 and NR2 acidic reaction centers (C) were 16.9 kcal/mol and 0.87, respectively. The calculated HLCs of ions were compared to the HLCs of 142 ions calculated by quantum mechanics. Effects of inter-molecular interaction of the monopoles with polarizability, dipole, H-bonding, and resonance on acidity of the solutes in the gas phase are discussed. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Analysis of nucleotides and oligonucleotides immobilized as self-assembled monolayers by static secondary ion mass spectrometry.

PubMed

Patrick, J S; Cooks, R G; Pachuta, S J

1994-11-01

Nucleic acid constituents can be bound to a metal surface in the form of self-assembled monolayers. Binding is achieved either through ionic interactions with a self-assembled 2-aminoethanethiol monolayer or by direct covalent binding of a dithiophosphate oligonucleotide to a metal surface through a sulfur-metal bond. Nucleotides, polynucleotides (both normal and a dithiophosphate analog) and double-stranded DNA have all been bound to surfaces. When the surfaces are interrogated using static secondary ion mass spectrometry (SIMS), the surface-bound nucleic acid constituents are observed in the form of the characteristic protonated nucleic acid base ions (BH2+). While a silver foil substrate was found to provide the highest absolute signal, vapor-deposited gold yields the best signal-to-noise ratio for ionically bound deoxyguanosine monophosphate. Under comparable conditions, a Cs+ projectile produces a 10-fold increase in the secondary ion signal relative to a Ga+ projectile. The experiment has been extended to a triple-quadrupole instrument where tandem mass spectrometric experiments on ionically immobilized dGMP showed the characteristic loss of ammonia from the released BH2+ ion. When a 'biomimetic' surface formed by ionically immobilizing double-stranded DNA is exposed to a solution containing ethidium bromide, ions corresponding to the non-covalent adduct are readily detectable using SIMS. This adduct and the nucleic acid constituents can be monitored at levels below 10 fmol.

Recent development of ionic liquid stationary phases for liquid chromatography.

PubMed

Shi, Xianzhe; Qiao, Lizhen; Xu, Guowang

2015-11-13

Based on their particular physicochemical characteristics, ionic liquids have been widely applied in many fields of analytical chemistry. Many types of ionic liquids were immobilized on a support like silica or monolith as stationary phases for liquid chromatography. Moreover, different approaches were developed to bond covalently ionic liquids onto the supporting materials. The obtained ionic liquid stationary phases show multi-mode mechanism including hydrophobic, hydrophilic, hydrogen bond, anion exchange, π-π, and dipole-dipole interactions. Therefore, they could be used in different chromatographic modes including ion-exchange, RPLC, NPLC and HILIC to separate various classes of compounds. This review mainly summarizes the immobilized patterns and types of ionic liquid stationary phases, their retention mechanisms and applications in the recent five years. Copyright © 2015 Elsevier B.V. All rights reserved.

Model Systems of Precursor Cellular Membranes: Long-Chain Alcohols Stabilize Spontaneously Formed Oleic Acid Vesicles

PubMed Central

Rendón, Adela; Carton, David Gil; Sot, Jesús; García-Pacios, Marcos; Montes, Ruth; Valle, Mikel; Arrondo, José-Luis R.; Goñi, Felix M.; Ruiz-Mirazo, Kepa

2012-01-01

Oleic acid vesicles have been used as model systems to study the properties of membranes that could be the evolutionary precursors of more complex, stable, and impermeable phospholipid biomembranes. Pure fatty acid vesicles in general show high sensitivity to ionic strength and pH variation, but there is growing evidence that this lack of stability can be counterbalanced through mixtures with other amphiphilic or surfactant compounds. Here, we present a systematic experimental analysis of the oleic acid system and explore the spontaneous formation of vesicles under different conditions, as well as the effects that alcohols and alkanes may have in the process. Our results support the hypothesis that alcohols (in particular 10- to 14-C-atom alcohols) contribute to the stability of oleic acid vesicles under a wider range of experimental conditions. Moreover, studies of mixed oleic-acid-alkane and oleic-acid-alcohol systems using infrared spectroscopy and Langmuir trough measurements indicate that precisely those alcohols that increased vesicle stability also decreased the mobility of oleic acid polar headgroups, as well as the area/molecule of lipid. PMID:22339864

PCE solubilization and mobilization by commercial humic acid

NASA Astrophysics Data System (ADS)

Johnson, William P.; John, W. Wynn

1999-01-01

In this paper, comparison is made of terms describing solubilization of hydrophobic organic compounds (HOC) by dissolved humic substances (DHS) and commercial non-ionic surfactants. This paper examines the ability of a commercial humic acid (Aldrich humic acid) to solubilize and mobilize tetrachlorothene (PCE) residual in porous media. The constant for solubilization of PCE by Aldrich humic acid is shown to be a factor of two to thirty times less than that published for dodecyl alcohol ethoxylate surfactants, showing that Aldrich humic acid is less capable than some non-ionic surfactants at solubilizing residual PCE. The depression of PCE-water interfacial tension in the presence of DHS is shown to be significantly less than published values for a non-ionic surfactant, and surfactant mixtures, indicating that the DHS used in this study is less prone to cause mobilization of non-aqueous phase liquids relative to surfactants. Several possible advantages of DHS use in the remediation of subsurface media contaminated with HOC are described, including the ability of DHS to solubilize HOC irrespective of the DHS concentration, and potential lesser tendency of DHS to depress the interfacial tension between non-aqueous phases and water relative to surfactants (an advantage when mobilization is undesired).

[Relation between location of elements in periodic table and affinity for the malignant tumor (author's transl)].

PubMed

Ando, A; Hisada, K; Ando, I

1977-10-01

Affinity of many inorganic compounds for the malignant tumor was examined, using the rats which were subcutaneously transplanted with Yoshida sarcoma. And the relations between the uptake rate into the malignant tumor and in vitro binding power to the protein were investigated in these compounds. In these experiments, the bipositive ions and anions had not affinity for the tumor tissue with a few exceptions. On the other hand, Hg, Au and Bi, which have strong binding power to the protein, showed high uptake rate into the malignant tumor. As Hg++, Au+ and Bi+++ are soft acids according to classification of Lewis acids, it was thought that these elements would bind strongly to soft base (R-SH, R-S-) present in the tumor tissue. In many hard acids (according to classification of Lewis acids), the uptake rate into the tumor was shown as a function of ionic potentials (valency/ionic radii) of the metal ions. It is presumed that the chemical bond of these hard acids in the tumor tissue is ionic bond to hard base (R-COO-, R-PO3(2-), R-SO3-, R-NH2).

Relation between the location of elements in the periodic table and tumor-uptake rate.

PubMed

Ando, A; Ando, I; Hiraki, T; Hisada, K

1985-01-01

The bipositive ions and anions, with few exceptions, indicated a low tumor uptake rate. On the other hand, compounds of Hg, Au and Bi, which have a strong binding power to protein, showed a high tumor uptake rate. As Hg2+, Au+ and Bi3+ are soft acids according to the classification of Lewis acids, it was thought that these ions would bind strongly to soft bases (R-SH, R-S-) present in tumor tissue. For many hard acids such as 85Sr2+, 67Ga3+, 181Hf4+, and 95Nb5+, tumor uptake rates are shown as a function of ionic potentials (valency/ionic radii) of the metal ions. Considering the present data and previously reported results, it was presumed that hard acids of trivalence, quadrivalence and pentavalence would replace calcium in the calcium salts of hard bases (calcium salts of acid mucopolysaccharides, etc.). Ionic potentials of alkaline metals and Tl were small, but the tumor-uptake rate of these elements indicated various values. As Ge and Sb are bound by covalent bonds to chloride, GeCl4 and SbCl3 behaved differently from many metallic compounds in tumor tissue.

Application of ionic liquids based enzyme-assisted extraction of chlorogenic acid from Eucommia ulmoides leaves.

PubMed

Liu, Tingting; Sui, Xiaoyu; Li, Li; Zhang, Jie; Liang, Xin; Li, Wenjing; Zhang, Honglian; Fu, Shuang

2016-01-15

A new approach for ionic liquid based enzyme-assisted extraction (ILEAE) of chlorogenic acid (CGA) from Eucommia ulmoides is presented in which enzyme pretreatment was used in ionic liquids aqueous media to enhance extraction yield. For this purpose, the solubility of CGA and the activity of cellulase were investigated in eight 1-alkyl-3-methylimidazolium ionic liquids. Cellulase in 0.5 M [C6mim]Br aqueous solution was found to provide better performance in extraction. The factors of ILEAE procedures including extraction time, extraction phase pH, extraction temperatures and enzyme concentrations were investigated. Moreover, the novel developed approach offered advantages in term of yield and efficiency compared with other conventional extraction techniques. Scanning electronic microscopy of plant samples indicated that cellulase treated cell wall in ionic liquid solution was subjected to extract, which led to more efficient extraction by reducing mass transfer barrier. The proposed ILEAE method would develope a continuous process for enzyme-assisted extraction including enzyme incubation and solvent extraction process. In this research, we propose a novel view for enzyme-assisted extraction of plant active component, besides concentrating on enzyme facilitated cell wall degradation, focusing on improvement of bad permeability of ionic liquids solutions. Copyright © 2015 Elsevier B.V. All rights reserved.

Crystal Structure and Properties of Imidazo-Pyridine Ionic Liquids.

PubMed

Farren-Dai, Marco; Cameron, Stanley; Johnson, Michel B; Ghandi, Khashayar

2018-07-05

Computational studies were performed on novel protic ionic liquids imidazolium-[1,2-a]-pyridine trifluoroacetate [ImPr][TFA] synthesized by the reaction of imidazo-[1,2a]-pyridine (ImPr) with trifluoroacetic acid (TFA), and on fused salt imidazolium-[1,2-a]-pyridine maleamic carbonate [ImPr][Mal] synthesized by reaction of ImPr with maleamic acid (Mal). Synthesis was performed as one-pot reactions, which applies green chemistry tenets. Both these compounds begin to decompose at 180°C. Our computational studies suggest another thermal reaction channel, in which [ImPr][Mal] can also thermally polymerizes to polyacrylamide which then cyclizes. This is thermal product remains stable up to 700 degrees, consistent with our thermogravimetric studies. [ImPr][TFA] exhibited good conductivity and ideal ionic behavior, as evaluated by a Walden plot. X-ray crystallography of [ImPr][TFA] revealed a tightly packed system for the crystals as a result of strong ionic interaction, pi-stacking, and fluorine-CH interactions. Both synthesized compounds exhibited some CO 2 absorptivity, with [ImPr][Mal] outperforming [ImPr][TFA] in this regard. The quantum chemistry based computational methods can shed light on many properties of these ionic liquids, but they are challenged in fully describing their ionic nature. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Effects of molten-salt/ionic-liquid mixture on extraction of docosahexaenoic acid (DHA)-rich lipids from Aurantiochytrium sp. KRS101.

PubMed

Choi, Sun-A; Jung, Joo-Young; Kim, Kyochan; Kwon, Jong-Hee; Lee, Jin-Suk; Kim, Seung Wook; Park, Ji-Yeon; Yang, Ji-Won

2014-11-01

In this study, lipid extraction from Aurantiochytrium sp. was performed using a molten-salt/ionic-liquid mixture. The total fatty acid content of Aurantiochytrium sp. was 478.8 mg/g cell, from which 145 mg/g cell (30.3% of total fatty acids) of docosahexaenoic acid (DHA) was obtained. FeCl3·6H2O showed a high lipid extraction yield (207.9 mg/g cell), when compared with that of [Emim]OAc, which was only 118.1 mg/g cell; notably however, when FeCl3·6H2O was mixed with [Emim]OAc (5:1, w/w), the yield was increased to 478.6 mg/g cell. When lipid was extracted by the FeCl3·6H2O/[Emim]OAc mixture at a 5:1 (w/w) blending ratio under 90 °C, 30 min reaction conditions, the fatty acid content of the extracted lipid was a high purity 997.7 mg/g lipid, with most of the DHA having been extracted (30.2% of total fatty acids). Overall, lipid extraction from Aurantiochytrium sp. was enhanced by the synergistic effects of the molten-salt/ionic-liquid mixture with different ions.

A novel ionic liquid-modified organic-polymer monolith as the sorbent for in-tube solid-phase microextraction of acidic food additives.

PubMed

Wang, Ting-Ting; Chen, Yi-Hui; Ma, Jun-Feng; Hu, Min-Jie; Li, Ying; Fang, Jiang-Hua; Gao, Hao-Qi

2014-08-01

A novel ionic liquid-modified organic-polymer monolithic capillary column was prepared and used for in-tube solid-phase microextraction (SPME) of acidic food additives. The primary amino group of 1-aminopropyl-3-methylimidazolium chloride was reacted with the epoxide group of glycidyl methacrylate. The as-prepared new monomer was then copolymerized in situ with acrylamide and N,N'-methylenebisacrylamide in the presence of polyethylene glycol (PEG)-8000 and PEG-10,000 as porogens. The extraction performance of the developed monolithic sorbent was evaluated for benzoic acid, 3-hydroxybenzoic acid, cinnamic acid, 2,4-dichlorophenoxyacetic acid, and 3-(trifluoromethyl)-cinnamic acid. Such a sorbent, bearing hydrophobic and anion-exchange groups, had high extraction efficiency towards the test compounds. The adsorption capacities for the analytes dissolved in water ranged from 0.18 to 1.74 μg cm(-1). Good linear calibration curves (R(2) > 0.99) were obtained, and the limits of detection (S/N = 3) for the analytes were found to be in the range 1.2-13.5 ng mL(-1). The recoveries of five acidic food additives spiked in Coca-Cola beverage samples ranged from 85.4 % to 98.3 %, with RSD less than 6.9 %. The excellent applicability of the ionic liquid (IL)-modified monolithic column was further tested by the determination of benzoic acid content in Sprite samples, further illustrating its good potential for analyzing food additives in complex samples.

Kinetics of nonoxidative leaching of galena in perchloric, hydrobromic, and hydrochloric acid solutions

NASA Astrophysics Data System (ADS)

Núñez, C.; Espiell, F.; García-Zayas, J.

1988-08-01

Several kinetic studies are presented on the nonoxidative leaching of galena with solutions of hydrocloric, hydrobromic, and perchloric acid. The kinetic parameters were set up in terms of the mean ionic activities of the electrolytes. The apparent order of reaction for the mean ionic activity of perchloric acid is one. For hydrochloric acid the order of reaction over a wide range of concentrations is 3/2 with respect to its mean activity. For hydrobromic acid, whose anion has greater complex-forming power for lead than HC1, the order of reaction is 2. Activation energies are 64.4 kJ/mole for HC1, 71.5 kJ/mole for HC104, and 66.5 kJ mole for HBr. The complete kinetic equations are given for the three reactions.

Structural and morphological changes in supramolecular-structured polymer electrolyte membrane fuel cell on addition of phosphoric acid

NASA Astrophysics Data System (ADS)

Hendrana, S.; Pryliana, R. F.; Natanael, C. L.; Rahayu, I.

2018-03-01

Phosphoric acid is one agents used in membrane fuel cell to modify ionic conductivity. Therefore, its distribution in membrane is a key parameter to gain expected conductivity. Efforts have been made to distribute phosphoric acid in a supramolecular-structured membrane prepared with a matrix. To achieve even distribution across bulk of the membrane, the inclusion of the polyacid is carried out under pressurized chamber. Image of scanning electron microscopy (SEM) shows better phosphoric acid distribution for one prepared in pressurized state. It also leads in better performing in ionic conductivity. Moreover, data from differential scanning calorimetry (DSC) indicate that the addition of phosphoric acid is prominent in the change of membrane structure, while morphological changes are captured in SEM images.

Effect of salts on the kinetic parameters and thermal stability of bovine brain acid phosphatase.

PubMed

Bittencourt, H M; Chaimovich, H

1976-08-01

Bovine brain acid phosphatase is inhibited, at any pH, by an increase in ionic strength. The rate decrease is associated at pH 5, with a marked decrease in Km and, at pH 8, with a noticeable decrease in Vm. The rate of thermal inactivation of the enzyme is unaffected by increasing ionic strength up to 300 mM. These results are discussed in terms of interactions at the active site of the enzyme.

Ionic strength and DOC determinations from various freshwater sources to the San Francisco Bay

USGS Publications Warehouse

Hunter, Y.R.; Kuwabara, J.S.

1994-01-01

An exact estimation of dissolved organic carbon (DOC) within the salinity gradient of zinc and copper metals is significant in understanding the limit to which DOC could influence metal speciation. A low-temperature persulfate/oxygen/ultraviolet wet oxidation procedure was utilized for analyzing DOC samples adapted for ionic strength from major freshwater sources of the northern and southern regions of San Francisco Bay. The ionic strength of samples was modified with a chemically defined seawater medium up to 0.7M. Based on the results, a minimum effect of ionic strength on oxidation proficiency for DOC sources to the Bay over an ionic strength gradient of 0.0 to 0.7 M was observed. There was no major impacts of ionic strength on two Suwanee River fulvic acids. In general, the noted effects associated with ionic strength were smaller than the variances seen in the aquatic environment between high- and low-temperature methods.

Hollow fiber supported ionic liquid membrane microextraction for determination of sulfonamides in environmental water samples by high-performance liquid chromatography.

PubMed

Tao, Yong; Liu, Jing-Fu; Hu, Xia-Lin; Li, Hong-Cheng; Wang, Thanh; Jiang, Gui-Bin

2009-08-28

By using ionic liquid as membrane liquid and tri-n-octylphosphine oxide (TOPO) as additive, hollow fiber supported liquid phase microextraction (HF-LPME) was developed for the determination of five sulfonamides in environmental water samples by high-performance liquid chromatography with ultraviolet detection The extraction solvent and the parameters affecting the extraction enrichment factor such as the type and amount of carrier, pH and volume ratio of donor phase and acceptor phase, extraction time, salt-out effect and matrix effect were optimized. Under the optimal extraction conditions (organic liquid membrane phase: [C(8)MIM][PF(6)] with 14% TOPO (w/v); donor phase: 4mL, pH 4.5 KH(2)PO(4) with 2M Na(2)SO(4); acceptor phase: 25microL, pH 13 NaOH; extraction time: 8 h), low detection limits (0.1-0.4microg/L, RSDor=0.999) were obtained for all the analytes. The presence of humic acid (0-25mg/L dissolved organic carbon) and bovine serum albumin (0-100microg/mL) had no significant effect on the extraction efficiency. Good spike recoveries over the range of 82.2-103.2% were obtained when applying the proposed method on five real environmental water samples. These results indicated that this present method was very sensitive and reliable with good repeatabilities and excellent clean-up in water samples. The proposed method confirmed hollow fiber supported ionic liquid membrane based LPME to be robust to monitoring trace levels of sulfadiazine, sulfamerazine, sulfamethazine, sulfadimethoxine and sulfamethoxazole in aqueous samples.

Ionic liquid [OMIm][OAc] directly inducing oxidation cleavage of the β-O-4 bond of lignin model compounds.

PubMed

Yang, Yingying; Fan, Honglei; Meng, Qinglei; Zhang, Zhaofu; Yang, Guanying; Han, Buxing

2017-08-03

We explored the oxidation reactions of lignin model compounds directly induced by ionic liquids under metal-free conditions. In this work, it was found that ionic liquid 1-octyl-3-methylimidazolium acetate as a solvent could promote the aerobic oxidation of lignin model compound 2-phenoxyacetophenone (1) and the yields of phenol and benzoic acid from 1 could be as high as 96% and 86%, respectively. A possible reaction pathway was proposed based on a series of control experiments. An acetate anion from the ionic liquid attacked the hydrogen from the β-carbon thereby inducing the cleavage of the C-O bond of the aromatic ether. Furthermore, it was found that 2-(2-methoxyphenoxy)-1-phenylethanone (4) with a methoxyl group could also be transformed into aromatic products in this simple reaction system and the yields of phenol and benzoic acid from 4 could be as high as 98% and 85%, respectively. This work provides a simple way for efficient transformation of lignin model compounds.

Ionic Liquid-Hybrid Molecularly Imprinted Material-Filter Solid-Phase Extraction Coupled with HPLC for Determination of 6-Benzyladenine and 4-Chlorophenoxyacetic Acid in Bean Sprouts.

PubMed

Han, Yehong; Yang, Chunliu; Zhou, Yang; Han, Dandan; Yan, Hongyuan

2017-03-01

A new method involving ionic liquid-hybrid molecularly imprinted material-filter solid-phase extraction coupled to high-performance liquid chromatography (IL-HIM-FSPE-HPLC) was developed for the simultaneous isolation and determination of 6-benzyladenine (6-BA) and 4-chlorophenoxyacetic acid (4-CPA) in bean sprouts. Sample preconcentration was performed using a modified filter, with the new IL-HIM as the adsorbent, which shows double adsorption. The first adsorption involves special recognition of molecular imprinting, and the second involves ion exchange and electrostatic attraction caused by the ionic liquid. This method combines the advantages of ionic liquids, hybrid materials, and molecularly imprinted polymers and was successfully applied to determine 6-BA and 4-CPA in bean sprouts. The adsorption of 6-BA to IL-HIM is based on selective imprinted recognition, whereas the adsorption of 4-CPA is mainly dependent on ion-exchange interactions.

Ionic liquids as advantageous solvents for headspace gas chromatography of compounds with low vapor pressure.

PubMed

Andre, M; Loidl, J; Laus, G; Schottenberger, H; Bentivoglio, G; Wurst, K; Ongania, K-H

2005-01-15

The potential of ionic liquids as solvents for headspace gas chromatography was investigated. Three compounds with boiling points above 200 degrees C were selected to demonstrate the feasibility of the concept described. 2-Ethylhexanoic acid, formamide, and tri-n-butylamine as examples of acidic, neutral, and basic analytes were dissolved in acidic 1-n-butyl-3-methylimidazolium hydrogen sulfate (1), neutral 1-n-butyl-2,3-dimethylimidazolium dicyanamide (2), and 2 containing 1,8-diazabicyclo[5.4.0]undec-7-ene to adjust basic conditions. All analytes could be determined with limits of detection and limits of quantification in the low-ppm concentration range.

A novel conductance glucose biosensor in ultra-low ionic strength solution triggered by the oxidation of Ag nanoparticles.

PubMed

Song, Yonghai; Chen, Jingyi; Liu, Hongyu; Li, Ping; Li, Hongbo; Wang, Li

2015-09-03

A simple, sensitive and effective method to detect glucose in ultra-low ionic strength solution containing citrate-capped silver nanoparticles (CCAgNPs) was developed by monitoring the change of solution conductance. Glucose was catalyzed into gluconic acid firstly by glucose oxidase in an O2-saturated solution accompanied by the reduction of O2 into hydrogen peroxide (H2O2). Then, CCAgNPs was oxidized by H2O2 into Ag(+) and the capping regent of citrate was released at the same time. All these resulted Ag(+), gluconic acid and the released citrate would contribute to the increase of solution ionic strength together, leading to a detectable increase of solution conductance. And a novel conductance glucose biosensor was developed with a routine linear range of 0.06-4.0 mM and a suitable detection limit of 18.0 μM. The novel glucose biosensor was further applied in energy drink sample and proven to be suitable for practical system with low ionic strength. The proposed conductance biosensor achieved a significant breakthrough of glucose detection in ultra-low ionic strength media. Copyright © 2015 Elsevier B.V. All rights reserved.

Interaction and dynamics of ionic liquids based on choline and amino acid anions

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

Campetella, M.; Bodo, E., E-mail: enrico.bodo@uniroma1.it; Caminiti, R., E-mail: ruggero.caminiti@uniroma1.it

2015-06-21

The combination of amino acid anions with the choline cation gives origin to a new and potentially important class of organic ionic liquids that might represent a viable and bio-compatible alternative with respect to the traditional ones. We present here a detailed study of the bulk phase of the prototype system composed of the simplest amino acid (alanine) anion and the choline cation, based on ab initio and classical molecular dynamics. Theoretical findings have been validated by comparing with accurate experimental X-ray diffraction data and infrared spectra. We find that hydrogen bonding (HB) features in these systems are crucial inmore » establishing their local geometric structure. We have also found that these HBs once formed are persistent and that the proton resides exclusively on the choline cation. In addition, we show that a classical force field description for this particular ionic liquid can be accurately performed by using a slightly modified version of the generalized AMBER force field.« less

Interaction and dynamics of ionic liquids based on choline and amino acid anions

NASA Astrophysics Data System (ADS)

Campetella, M.; Bodo, E.; Caminiti, R.; Martino, A.; D'Apuzzo, F.; Lupi, S.; Gontrani, L.

2015-06-01

The combination of amino acid anions with the choline cation gives origin to a new and potentially important class of organic ionic liquids that might represent a viable and bio-compatible alternative with respect to the traditional ones. We present here a detailed study of the bulk phase of the prototype system composed of the simplest amino acid (alanine) anion and the choline cation, based on ab initio and classical molecular dynamics. Theoretical findings have been validated by comparing with accurate experimental X-ray diffraction data and infrared spectra. We find that hydrogen bonding (HB) features in these systems are crucial in establishing their local geometric structure. We have also found that these HBs once formed are persistent and that the proton resides exclusively on the choline cation. In addition, we show that a classical force field description for this particular ionic liquid can be accurately performed by using a slightly modified version of the generalized AMBER force field.

Recent Development in Chemical Depolymerization of Lignin: A Review

DOE PAGES

Wang, Hai; Tucker, Melvin; Ji, Yun

2013-01-01

This article reviewed recent development of chemical depolymerization of lignins. There were five types of treatment discussed, including base-catalyzed, acid-catalyzed, metallic catalyzed, ionic liquids-assisted, and supercritical fluids-assisted lignin depolymerizations. The methods employed in this research were described, and the important results were marked. Generally, base-catalyzed and acid-catalyzed methods were straightforward, but the selectivity was low. The severe reaction conditions (high pressure, high temperature, and extreme pH) resulted in requirement of specially designed reactors, which led to high costs of facility and handling. Ionic liquids, and supercritical fluids-assisted lignin depolymerizations had high selectivity, but the high costs of ionic liquids recyclingmore » and supercritical fluid facility limited their applications on commercial scale biomass treatment. Metallic catalyzed depolymerization had great advantages because of its high selectivity to certain monomeric compounds and much milder reaction condition than base-catalyzed or acid-catalyzed depolymerizations. It would be a great contribution to lignin conversion if appropriate catalysts were synthesized.« less

Improved electrolyte for zinc-bromine flow batteries

NASA Astrophysics Data System (ADS)

Wu, M. C.; Zhao, T. S.; Wei, L.; Jiang, H. R.; Zhang, R. H.

2018-04-01

Conventional zinc bromide electrolytes offer low ionic conductivity and often trigger severe zinc dendrite growth in zinc-bromine flow batteries. Here we report an improved electrolyte modified with methanesulfonic acid, which not only improves the electrolyte conductivity but also ameliorates zinc dendrite. Experimental results also reveal that the kinetics and reversibility of Zn2+/Zn and Br2/Br- are improved in this modified electrolyte. Moreover, the battery's internal resistance is significantly reduced from 4.9 to 2.0 Ω cm2 after adding 1 M methanesulfonic acid, thus leading to an improved energy efficiency from 64% to 75% at a current density of 40 mA cm-2. More impressively, the battery is capable of delivering an energy efficiency of about 78% at a current density of as high as 80 mA cm-2 when the electrode is replaced by a thermally treated one. Additionally, zinc dendrite growth is found to be effectively suppressed in methanesulfonic acid supported media, which, as a result, enables the battery to be operated for 50 cycles without degradation, whereas the one without methanesulfonic acid suffers from significant decay after only 40 cycles, primarily due to severe zinc dendrite growth. These superior results indicate methanesulfonic acid is a promising supporting electrolyte for zinc-bromine flow batteries.

I. Synthesis, characterization, and base catalysis of novel zeolite supported super-basic materials II. Oxidative dehydrogenation of ethane over reduced heteropolyanion catalysts

NASA Astrophysics Data System (ADS)

Galownia, Jonathan M.

This thesis is composed of two separate and unrelated projects. The first part of this thesis outlines an investigation into the synthesis and characterization of a novel zeolite supported super-base capable of carbon-carbon olefin addition to alkyl aromatics. A zeolite supported basic material capable of such reactions would benefit many fine chemical syntheses, as well as vastly improve the economics associated with production of the high performance thermoplastic polyester polyethylene naphthalate. The thermal decomposition of alkali---metal azides impregnated in zeolite X is investigated as a novel route to the synthesis of a zeolite supported super-base. Impregnation of the alkali---metal azide precursor is shown to result in azide species occluded within the pores of the zeolite support by using high speed, solid-state 23Na MAS and 2D MQMAS NMR, FTIR, and TGA characterization methods. Addition of alkali---metal azides to the zeolite results in redistribution of the extra-lattice cations in the zeolite framework. Thermal decomposition of impregnated azide species produces further cation redistribution, but no neutral metallic clusters are detected by high speed, solid-state 23Na MAS NMR following thermal activation of the materials. Instead, it is possible that inactive ionic clusters are formed. The thermally activated materials do not promote base catalysis for the isomerization of 1-butene, the ethylation of toluene and o-xylene, and the alkenylation of o-xylene with 1,3-butadiene to produce 5-ortho-tolyl-pent-2-ene (5-OTP). The lack of catalytic activity in the materials is attributed to failure of the materials to form neutral metallic clusters during thermal treatment, possibly due to preferential formation of NMR silent ionic clusters. The formation of neutral metallic clusters is found to be insensitive to synthesis technique and activation procedure. It is concluded that the impregnation of alkali---metal azides in zeolite X does not provide a reliable precursor for the formation of zeolite supported super-basic materials. The second part of this thesis describes the oxidative dehydrogenation of ethane over partially reduced heteropolyanions. Niobium and pyridine exchanged salts of phosphomolybdic (NbPMo12Pyr) and phosphovanadomolybdic (NbPMo11VPyr) acids are investigated as catalyst precursors to prepare materials for catalyzing the oxidative dehydrogenation of ethane to ethylene and acetic acid at atmospheric pressure. The effects of feed composition, steam flow, temperature, and precursor composition on catalytic activity and selectivity are presented for both ethane and ethylene oxidation. Production of ethylene and acetic acid from ethane using the catalytic materials exceeds that reported in the literature for Mo-V-Nb-Ox systems under atmospheric or elevated pressure. Production of acetic acid from ethylene is also greater than that observed for Mo-V-Nb-Ox systems. Addition of vanadium reduces catalytic activity and selectivity to both ethylene and acetic acid while niobium is essential for the formation of acetic acid from ethane. Other metals such as antimony, iron, and gallium do not provide the same beneficial effect as niobium. Molybdenum in close proximity to niobium is the active site for ethane activation while niobium is directly involved in the transformation of ethylene to acetic acid. A balance of niobium and protonated pyridine is required to produce an active catalyst. Water is found to aid in desorption of acetic acid, thereby limiting deep oxidation to carbon oxides. A reaction scheme is proposed for the production of acetic acid from ethane over the catalytic materials.

Induction of Ca2+-dependent cyclosporin A-insensitive nonspecific permeability of the inner membrane of liver mitochondria and cytochrome c release by α,ω-hexadecanedioic acid in media of varying ionic strength.

PubMed

Dubinin, M V; Vedernikov, A A; Khoroshavina, E I; Samartsev, V N

2014-06-01

In liver mitochondria loaded with Ca2+ or Sr(2+), α,ω-hexadecanedioic acid (HDA) can induce nonspecific permeability of the inner membrane (mitochondrial pore) by the mechanism insensitive to cyclosporin A (CsA). In this work we studied the effect of ionic strength of the incubation medium on the kinetics of the processes that accompany Ca2+-dependent induction of the mitochondrial pore by fatty acid: organelle swelling, Ca2+ release from the matrix, changes in transmembrane potential (Δψ) and rate of oxygen consumption, and the release of cytochrome c from the intermembrane space. Two basic incubation media were used: sucrose medium and isotonic ionic medium containing KCl without sucrose. We found that 200 μM Ca2+ and 20 μM HDA in the presence of CsA effectively induce high-amplitude swelling of mitochondria both in the case of sucrose and in the ionic incubation medium. In the presence of CsA, mitochondria can rapidly absorb Ca2+ and retain it in the matrix for a while without reducing Δψ. Upon incubation in the ionic medium, mitochondria retain most of the added Ca2+ in the matrix for a short time without reducing the Δψ. In both cases the addition of HDA to the mitochondria 2 min after the introduction of Ca2+ leads to the rapid release of these ions from the matrix and total drop in Δψ. The mitochondrial swelling induced by Ca2+ and HDA in non-ionic medium is accompanied by almost maximal stimulation of respiration. Under the same conditions, but during incubation of mitochondria in the ionic medium, it is necessary to add cytochrome c for significant stimulation of respiration. The mitochondrial swelling induced by Ca2+ and HDA leads to the release of cytochrome c in a larger amount in the case of ionic medium than for the sucrose medium. We conclude that high ionic strength of the incubation medium determines the massive release of cytochrome c from mitochondria and liberates it from the respiratory chain, which leads to blockade of electron transport along the respiratory chain and consequently to disruption of the energy functions of the organelles.

Ions in Wine and Their Relation to Electrical Conductivity Under Ultrasound Irradiation.

PubMed

Yan, Yan-Ying; Zhang, Qing-An; Li, Er-Chun; Zhang, Ya-Feng

2017-09-01

Change in electrical conductivity is considered a potential indicator for the on-line monitoring of wine aging accelerated by ultrasound, as determined in our previous study; however, the exact mechanism of change is currently unclear. In this study, the ion content and the total ionic strength were analyzed by ion-exchange chromatography to investigate the change mechanism of the electrical conductivity of wine under ultrasound irradiation. The results indicate that the changes in wine electrical conductivity during ultrasound treatment correlate with the changes in the cations (Na+, K+, Ca2+, Mg2+, and NH4+) and in the anions from the organic acids (malic acid, citric acid, tartaric acid, oxalic acid, and formic acid) and inorganic acids (Cl-, SO42-, and PO43-), especially for the ionic strength of the wine. Overall, electrical conductivity may be used to reflect the chemical reactions related to wine aging to a certain extent because the reactions can be initiated by the conversion of cations and by the degradation or auxiliary function of organic acids.

Application of ionic liquids based microwave-assisted simultaneous extraction of carnosic acid, rosmarinic acid and essential oil from Rosmarinus officinalis.

PubMed

Liu, Tingting; Sui, Xiaoyu; Zhang, Rongrui; Yang, Lei; Zu, Yuangang; Zhang, Lin; Zhang, Ying; Zhang, Zhonghua

2011-11-25

An ionic liquid based microwave-assisted simultaneous extraction and distillation (ILMSED) method has been developed for the effective extraction of carnosic acid (CA), rosmarinic acid (RA) and essential oil (EO) from Rosmarinus officinalis. A series of 1-alkyl-3-methylimidazolium ionic liquids differing in composition of anion and cation were evaluated for extraction yield in this work. The results obtained indicated that the anions and cations of ionic liquids had influences on the extraction of CA and RA, 1.0M 1-octyl-3-methylimidazolium bromide ([C8mim]Br) solution was selected as solvent. In addition, the ILMSED procedures for the three target ingredients were optimized and compared with other conventional extraction techniques. ILMSED gave the best result due to the highest extraction yield within the shortest extraction time for CA and RA. The novel process developed offered advantages in term of yield and selectivity of EO and shorter isolation time (20 min in comparison of 4h of hydrodistillation), and provides a more valuable EO (with high amount of oxygenated compounds). The microstructures and chemical structures of rosemary samples before and after extraction were also investigated. Moreover, the proposed method was validated by the stability, repeatability and recovery experiments. The results indicated that the developed ILMSED method provided a good alternative for the both extraction of non-volatile compounds (CA and RA) and EO from rosemary as well as other herbs. Copyright © 2011 Elsevier B.V. All rights reserved.

Highly efficient micellar extraction of toxic picric acid into novel ionic liquid: Effect of parameters, solubilization isotherm, evaluation of thermodynamics and design parameters.

PubMed

Bhatt, Darshak R; Maheria, Kalpana C; Parikh, Jigisha K

2015-12-30

A simple and new approach in cloud point extraction (CPE) method was developed for removal of picric acid (PA) by the addition of N,N,N,N',N',N'-hexaethyl-ethane-1,2-diammonium dibromide ionic liquid (IL) in non-ionic surfactant Triton X-114 (TX-114). A significant increase in extraction efficiency was found upon the addition of dicationic ionic liquid (DIL) at both nearly neutral and high acidic pH. The effects of different operating parameters such as pH, temperature, time, concentration of surfactant, PA and DIL on extraction of PA were investigated and optimum conditions were established. The extraction mechanism was also proposed. A developed Langmuir isotherm was used to compute the feed surfactant concentration required for the removal of PA up to an extraction efficiency of 90%. The effects of temperature and concentration of surfactant on various thermodynamic parameters were examined. It was found that the values of ΔG° increased with temperature and decreased with surfactant concentration. The values of ΔH° and ΔS° increased with surfactant concentration. The developed approach for DIL mediated CPE has proved to be an efficient and green route for extraction of PA from water sample. Copyright © 2015 Elsevier B.V. All rights reserved.

The chemical identity of intervessel pit membranes in Acer challenges hydrogel control of xylem hydraulic conductivity

PubMed Central

Klepsch, Matthias M.; Schmitt, Marco; Paul Knox, J.; Jansen, Steven

2016-01-01

Ion-mediated enhancement of the hydraulic conductivity of xylem tissue (i.e. the ionic effect) has been reported for various angiosperm species. One explanation of the ionic effect is that it is caused by the swelling and shrinking of intervessel pit membranes due to the presence of pectins and/or other cell-wall matrix polymers such as heteroxylans or arabinogalactan–proteins (AGPs) that may contain acidic sugars. Here, we examined the ionic effect for six Acer species and their pit membrane chemistry using immunocytochemistry, including antibodies against glycoproteins. Moreover, anatomical features related to the bordered pit morphology and vessel dimensions were investigated using light and electron microscopy. The ionic effect varied from 18 % (± 9) to 32 % (± 13). Epitopes of homogalacturonan (LM18) and xylan (LM11) were not detected in intervessel pit membranes. Negative results were also obtained for glycoproteins (extensin: LM1, JIM20; AGP glycan: LM2), although AGP (JIM13)-related epitopes were detected in parenchyma cells. The mean vessel length was significantly correlated with the magnitude of the ionic effect, unlike other pit or vessel-related characteristics. Our results suggest that intervessel pit membranes of Acer are unlikely to contain pectic or other acidic polysaccharides. Therefore, alternative explanations should be tested to clarify the ionic effect. PMID:27354661

The Role of Citric Acid in the Stabilization of Nanoparticles and Colloidal Particles in the Environment: Measurement of Surface Forces between Hafnium Oxide Surfaces in the Presence of Citric Acid.

PubMed

Shinohara, Shuhei; Eom, Namsoon; Teh, E-Jen; Tamada, Kaoru; Parsons, Drew; Craig, Vincent S J

2018-02-27

The interactions between colloidal particles and nanoparticles determine solution stability and the structures formed when the particles are unstable to flocculation. Therefore, knowledge of the interparticle interactions is important for understanding the transport, dissolution, and fate of particles in the environment. The interactions between particles are governed by the surface properties of the particles, which are altered when species adsorb to the surface. The important interactions in the environment are almost never those between the bare particles but rather those between particles that have been modified by the adsorption of natural organic materials. Citric acid is important in this regard not only because it is present in soil but also as a model of humic and fulvic acids. Here we have studied the surface forces between the model metal oxide surface hafnia in the presence of citric acid in order to understand the stability of colloidal particles and nanoparticles. We find that citric acid stabilizes the particles over a wide range of pH at low to moderate ionic strength. At high ionic strength, colloidal particles will flocculate due to a secondary minimum, resulting in aggregates that are dense and easily redispersed. In contrast, nanoparticles stabilized by citric acid remain stable at high ionic strengths and therefore exist in solution as individual particles; this will contribute to their dispersion in the environment and the uptake of nanoparticles by mammalian cells.

Efficient conversion of lignocellulosic biomass to levulinic acid using acidic ionic liquids.

PubMed

Khan, Amir Sada; Man, Zakaria; Bustam, Mohamad Azmi; Nasrullah, Asma; Ullah, Zahoor; Sarwono, Ariyanti; Shah, Faiz Ullah; Muhammad, Nawshad

2018-02-01

In the present research work, dicationic ionic liquids, containing 1,4-bis(3-methylimidazolium-1-yl) butane ([C 4 (Mim) 2 ]) cation with counter anions [(2HSO 4 )(H 2 SO 4 ) 0 ], [(2HSO 4 )(H 2 SO 4 ) 2 ] and [(2HSO 4 )(H 2 SO 4 ) 4 ] were synthesised. ILs structures were confirmed using 1 H NMR spectroscopy. Thermal stability, Hammett acidity, density and viscosity of ILs were determined. Various types of lignocellulosic biomass such as rubber wood, palm oil frond, bamboo and rice husk were converted into levulinic acid (LA). Among the synthesized ionic liquids, [C 4 (Mim) 2 ][(2HSO 4 )(H 2 SO 4 ) 4 ] showed higher % yield of LA up to 47.52 from bamboo biomass at 110°C for 60min, which is the better yield at low temperature and short time compared to previous reports. Surface morphology, surface functional groups and thermal stability of bamboo before and after conversion into LA were studied using SEM, FTIR and TGA analysis, respectively. This one-pot production of LA from agro-waste will open new opportunity for the conversion of sustainable biomass resources into valuable chemicals. Copyright © 2017 Elsevier Ltd. All rights reserved.

A Comparative Study of Phosphoric Acid-doped m-PBI Membranes

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

Perry, Kelly A; More, Karren Leslie; Payzant, E Andrew

2014-01-01

Phosphoric acid (PA)-doped m-polybenzimidazole (PBI) membranes used in high temperature fuel cells and hydrogen pumps were prepared by a conventional imbibing process and a sol-gel fabrication process. A comparative study was conducted to investigate the critical properties of PA doping levels, ionic conductivities, mechanical properties, and molecular ordering. This systematic study found that sol-gel PA-doped m-PBI membranes were able to absorb higher acid doping levels and to achieve higher ionic conductivities than conventionally imbibed membranes when treated in an equivalent manner. Even at similar acid loadings, the sol-gel membranes exhibited higher ionic conductivities. Heat treatment of conventionally imbibed membranes withmore » 29wt% solids caused a significant reduction in mechanical properties; conversely, sol-gel membranes exhibited an enhancement in mechanical properties. From X-ray structural studies and atomistic simulations, both conventionally imbibed and sol-gel membranes exhibited d-spacings of 3.5 and 4.6 , which were tentatively attributed to parallel ring stacking and staggered side-to-side packing, respectively, of the imidazole rings in these aromatic hetercyclic polymers. An anisotropic staggered side-to-side chain packing present in the conventional membranes may be root to the reduction in mechanical properties.« less

A novel electroanalytical approach based on the use of a room temperature ionic liquid for the determination of olive oil acidity.

PubMed

Baldo, M Antonietta; Oliveri, Paolo; Simonetti, Remo; Daniele, Salvatore

2016-12-01

In this paper, a novel voltammetric/amperometric approach for the direct determination of free acidity (FFA, expressed as mass percentage of free oleic acid) in olive oil samples is presented. The method is based on the reduction processes occurring at a platinum microdisk electrode involving the free fatty acids present in the matrices. To overcome problems related to the low conductivity of the samples investigated, olive oils were mixed with suitable amounts of the room temperature ionic liquid (RTIL), tri-hexyl(tetradecyl)phosphonium bis (trifluoromethylsulfonyl) imide ([P 14,6,6,6 ] + [NTf 2 ] - ), which acted as a supporting electrolyte. Conditions for a reliable quantification of the acids were preliminarily investigated by performing voltammetric and chronoamperometric measurements in RTIL solutions containing oleic acid at different concentrations. Oleic acid (OA) was chosen as a model compound as it is the main component of the FFA content in olive oils. In order to establish the effect of oxygen on the electroanalytical responses, the reduction process of OA was investigated under both deoxygenated and oxygenated conditions. It was found that, in both situations, the current arising from the electrode process of OA depended linearly on the OA concentration over a wide range varying from 0.1% to 8% OA (w/w). This range includes FFA values which can be found on all categories of commercially available oil samples, including extra-virgin, virgin and lampante oils. Voltammetric and chronoamperometric experiments were also performed in oil/RTIL samples artificially acidified (extra-virgin olive oils with known addition of oleic acid) and in natural olive oils from some commercial categories. The results obtained indicated that the electrochemical procedure developed was satisfactory in terms of both sensitivity and detection limits. The reliability of the proposed approach for the detection of FFA was finally assessed by comparison of the voltammetric/chronoamperometric values with those obtained by the official method for quantification of olive oil acidity, which is an acid/base volumetric titration. Copyright © 2016 Elsevier B.V. All rights reserved.

An efficient synthesis of 3,4-Dihydropyrimidin-2(1H)-ones and thiones catalyzed by a novel Brønsted acidic ionic liquid under solvent-free conditions.

PubMed

Zhang, Yonghong; Wang, Bin; Zhang, Xiaomei; Huang, Jianbin; Liu, Chenjiang

2015-02-26

We report here an efficient and green method for Biginelli condensation reaction of aldehydes, β-ketoesters and urea or thiourea catalyzed by Brønsted acidic ionic liquid [Btto][p-TSA] under solvent-free conditions. Compared to the classical Biginelli reaction conditions, the present method has the advantages of giving good yields, short reaction times, near room temperature conditions and the avoidance of the use of organic solvents and metal catalyst.

Synthesis and anti-microbial activity of hydroxylammonium ionic liquids.

PubMed

Ismail Hossain, M; El-Harbawi, Mohanad; Noaman, Yousr Abdulhadi; Bustam, Mohd Azmi B; Alitheen, Noorjahan Banu Mohamed; Affandi, Nor Azrin; Hefter, Glenn; Yin, Chun-Yang

2011-06-01

Eight hydroxylammonium-based room temperature ionic liquids (ILs) have been synthesized by acid-base neutralization of ethanolamines with organic acids. The ILs were characterized by infrared and nuclear magnetic resonance spectroscopies and elemental analysis. Their anti-microbial activities were determined using the well-diffusion method. All eight ILs were toxic to Staphylococcus aureus, while 2-hydroxyethylammonium lactate and 2-hydroxy-N-(2-hydroxyethyl)-N-methylethanaminium acetate showed high anti-microbial activity against a wide range of human pathogens. Crown Copyright © 2011. Published by Elsevier Ltd. All rights reserved.

pH dependence of the properties of waterborne pressure-sensitive adhesives containing acrylic acid.

PubMed

Wang, Tao; Canetta, Elisabetta; Weerakkody, Tecla G; Keddie, Joseph L; Rivas, Urko

2009-03-01

Polymer colloids are often copolymerized with acrylic acid monomers in order to impart colloidal stability. Here, the effects of the pH on the nanoscale and macroscopic adhesive properties of waterborne poly(butyl acrylate-co-acrylic acid) films are reported. In films cast from acidic colloidal dispersions, hydrogen bonding between carboxylic acid groups dominates the particle-particle interactions, whereas ionic dipolar interactions are dominant in films cast from basic dispersions. Force spectroscopy using an atomic force microscope and macroscale mechanical measurements show that latex films with hydrogen-bonding interactions have lower elastic moduli and are more deformable. They yield higher adhesion energies. On the other hand, in basic latex, ionic dipolar interactions increase the moduli of the dried films. These materials are stiffer and less deformable and, consequently, exhibit lower adhesion energies. The rate of water loss from acidic latex is slower, perhaps because of hydrogen bonding with the water. Therefore, although acid latex offers greater adhesion, there is a limitation in the film formation.

Superbase-derived protic ionic liquid extractants for metal ion separation

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

Bell, Jason R.; Dai, Sheng; Luo, Huimin

2014-04-19

Solvent extraction of La 3+ and Ba 2+ by an ionic liquid extractant in an imidazolium-based ionic liquid diluent was investigated. Seven protic ionic liquid extractants were examined and these protic ILs are based on five organic superbases and either 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octadione (Hfod) or 1,1,1,5,5,5-hexafluoroacetylacetone (Hhfac) -diketones as anion. For fod-based extractants, the extraction efficiencies and separation factors were found to be concentration dependent. The effects of aqueous phase acidity, extractant structure, and extractant concentration on separation properties of La 3+ and Ba 2+ are discussed in this paper.

Investigation of Proton Conductivity of Cation-Exchanged, Sulfonated Poly(b-Styrene-b-Isobutylene-b-Styrene) Membranes

DTIC Science & Technology

2009-09-01

solvents. Similar behavior was observed for Nafion -117 (also a polymer with ionic SO3H clusters) by other researchers (14). Results shown in this...pattern was only valid for ionic S-SIBS membranes exchanged with cations; neither acid form of SIBS-97-H nor Nafion -117 fell on this line. In order...10  vi INTENTIONALLY LEFT BLANK. 1 1. Introduction Research in ionic polymers has been gaining popularity in the scientific community

Humic Acid Effects on the Transport of Colloidal Particles in Unsaturated Porous Media: Humic Acid Dosage, pH, and Ionic Strength Dependence

NASA Astrophysics Data System (ADS)

Morales, V. L.; Gao, B.; Steenhuis, T. S.

2008-12-01

Soil colloids and biocolloids can facilitate contaminant transport within the soil profile through the complexation of pollutants previously thought to have limited mobility. Dissolved organic substances are qualitatively known to alter the behavior of colloids and surface chemistry of soil particles in aquatic environments when adsorbed to their surfaces. Specifically, it has been observed that even small amounts of adsorbed humic acids result in a pronounced increase in colloid mobility in saturated porous systems, presumably by a combination of electrostatic and steric stabilization. However, the degree to which adsorbed humic acids stabilize colloidal suspension is highly sensitive to the system's solution chemistry; mainly in terms of pH, ionic strength, and metal ions present. The objective of this study is to expound quantitatively on the role that combined stabilizing and destabilizing solution chemistry components have on humic acid-colloid transport in unsaturated media by isolating experimentally some underlying mechanisms that regulate colloid transport in realistic aquatic systems. We hypothesize that in chemically heterogeneous porous media, with ionic strength values above 0 and pH ranges from 4 to 9, the effect of humic acid on colloid suspensions cannot be simply characterized by increased stability and mobility. That a critical salt concentration must exists for a given humic acid concentration and pH, above which the network of humic acid collapses by forming coordination complexes with other suspended or adsorbed humic acids, thus increasing greatly the retention of colloids in the porous medium by sweep flocculation. In addition, capillary forces in unsaturated media may contribute further to overcome repulsive forces that prevent flocculation of humic acid-colloid complexes. The experimental work in this study will include: jar tests to determine critical solution concentration combinations for desired coagulation/flocculation rates, column experiments to obtain effluent breakthrough data, in-situ visualization of internal processes with bright field microscopy, batch adsorption measurements, and changes in hydrophobic interaction energy of colloid and media surfaces for realistic aqueous ionic strength and pH ranges. Such experimental results are expected to provide sufficient evidence to corroborate our speculations that under natural soil water conditions, humic acids may greatly contribute to the immobilization of colloidal particles.

Ionic and Covalent Stabilization of Intermediates and Transition States in Catalysis by Solid Acids

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

Deshlahra, Prashant; Carr, Robert T.; Iglesia, Enrique

Reactivity descriptors describe catalyst properties that determine the stability of kinetically relevant transition states and adsorbed intermediates. Theoretical descriptors, such as deprotonation energies (DPE), rigorously account for Brønsted acid strength for catalytic solids with known structure. Here, mechanistic interpretations of methanol dehydration turnover rates are used to assess how charge reorganization (covalency) and electrostatic interactions determine DPE and how such interactions are recovered when intermediates and transition states interact with the conjugate anion in W and Mo polyoxometalate (POM) clusters and gaseous mineral acids. Turnover rates are lower and kinetically relevant species are less stable on Mo than W POMmore » clusters with similar acid strength, and such species are more stable on mineral acids than that predicted from W-POM DPE–reactivity trends, indicating that DPE and acid strength are essential but incomplete reactivity descriptors. Born–Haber thermochemical cycles indicate that these differences reflect more effective charge reorganization upon deprotonation of Mo than W POM clusters and the much weaker reorganization in mineral acids. Such covalency is disrupted upon deprotonation but cannot be recovered fully upon formation of ion pairs at transition states. Predictive descriptors of reactivity for general classes of acids thus require separate assessments of the covalent and ionic DPE components. Here, we describe methods to estimate electrostatic interactions, which, taken together with energies derived from density functional theory, give the covalent and ionic energy components of protons, intermediates, and transition states. In doing so, we provide a framework to predict the reactive properties of protons for chemical reactions mediated by ion-pair transition states.« less

Aza-crown ether complex cation ionic liquids: preparation and applications in organic reactions.

PubMed

Song, Yingying; Cheng, Chen; Jing, Huanwang

2014-09-26

Aza-crown ether complex cation ionic liquids (aCECILs) were devised, fabricated, and characterized by using NMR spectroscopy, MS, thermogravimetric differential thermal analysis (TG-DTA), elemental analysis and physical properties. These new and room-temperature ILs were utilized as catalysts in various organic reactions, such as the cycloaddition reaction of CO2 to epoxides, esterification of acetic acid and alcohols, the condensation reaction of aniline and propylene carbonate, and Friedel-Crafts alkylation of indole with aldehydes were investigated carefully. In these reactions, the ionic liquid exhibited cooperative catalytic activity between the anion and cation. In addition, the aza-[18-C-6HK][HSO4]2 was the best acidic catalyst in the reactions of esterification and Friedel-Crafts alkylation under mild reaction conditions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The fish gill: site of action and model for toxic effects of environmental pollutants.

PubMed Central

Evans, D H

1987-01-01

The gill epithelium is the site of gas exchange, ionic regulation, acid-base balance, and nitrogenous waste excretion by fishes. The last three processes are controlled by passive and active transport of various solutes across the epithelium. Various environmental pollutants (e.g., heavy metals, acid rain, and organic xenobiotics) have been found to affect the morphology of the gill epithelium. Associated with these morphological pathologies, one finds alterations in blood ionic levels, as well as gill Na,K-activated ATPase activity and ionic fluxes. Such physiological disturbances may underly the toxicities of these pollutants. In addition, the epithelial transport steps which are affected in the fish gill model resemble those described in the human gut and kidney, sites of action of a variety of environmental toxins. Images FIGURE 1. a FIGURE 1. b FIGURE 3. PMID:3297663

Self-Supporting, Hydrophobic, Ionic Liquid-Based Reference Electrodes Prepared by Polymerization-Induced Microphase Separation.

PubMed

Chopade, Sujay A; Anderson, Evan L; Schmidt, Peter W; Lodge, Timothy P; Hillmyer, Marc A; Bühlmann, Philippe

2017-10-27

Interfaces of ionic liquids and aqueous solutions exhibit stable electrical potentials over a wide range of aqueous electrolyte concentrations. This makes ionic liquids suitable as bridge materials that separate in electroanalytical measurements the reference electrode from samples with low and/or unknown ionic strengths. However, methods for the preparation of ionic liquid-based reference electrodes have not been explored widely. We have designed a convenient and reliable synthesis of ionic liquid-based reference electrodes by polymerization-induced microphase separation. This technique allows for a facile, single-pot synthesis of ready-to-use reference electrodes that incorporate ion conducting nanochannels filled with either 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide or 1-dodecyl-3-methylimidazolium bis(trifluoromethyl sulfonyl)imide as ionic liquid, supported by a mechanically robust cross-linked polystyrene phase. This synthesis procedure allows for the straightforward design of various reference electrode geometries. These reference electrodes exhibit a low resistance as well as good reference potential stability and reproducibility when immersed into aqueous solutions varying from deionized, purified water to 100 mM KCl, while requiring no correction for liquid junction potentials.

State-of-the-Art pH Electrode Quality Control for Measurements of Acidic, Low Ionic Strength Waters.

ERIC Educational Resources Information Center

Stapanian, Martin A.; Metcalf, Richard C.

1990-01-01

Described is the derivation of the relationship between the pH measurement error and the resulting percentage error in hydrogen ion concentration including the use of variable activity coefficients. The relative influence of the ionic strength of the solution on the percentage error is shown. (CW)

Amino acid anions in organic ionic compounds. An ab initio study of selected ion pairs.

PubMed

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

2014-03-06

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

Composite fabrication and polymer modification using neoteric solvents

NASA Astrophysics Data System (ADS)

Eastman, Scott A.

This thesis is divided into two research initiatives: The fabrication and study of bulk, co-continuous, cellulosic-polymer composites with the aid of supercritical CO2 (SC CO2); and the study of poly(vinyl alcohol) (PVOH) modification and surface activity in ionic liquids. The first part of this thesis utilizes the tunable solubility, gas-like diffusivity, and omniphilic wettability of SC CO2 to incorporate and subsequently polymerize silicone and poly(enemer) prepolymer mixtures throughout various cellulosic substrates. Chapters two and three investigate the mechanical properties of these composites and demonstrate that nearly every resulting composite demonstrates an improved flexural modulus and energy release rate upon splitting. Fire resistance of these composites was also investigated and indicates that the heat release rate, total heat released, and char yield were significantly improved upon for all silicone composites compared to the untreated cellulosic material. Chapter four looks specifically at aspen-silicone composites for thermo-oxidative studies under applied loads in order to study the effect of silicone incorporation on the failure kinetics of aspen. The aspen-silicone composites tested under these conditions demonstrated significantly longer lifetimes under the same loading and heating conditions compared with untreated aspen. The second part of this thesis focuses on studying ionic liquids as potentially useful solvents and reaction media for poly(vinyl alcohol). Two ionic liquids (1-Butyl-3-methylimidizolium chloride and tributylethylphosphonium diethylphosphate) were found to readily dissolve PVOH. More importantly, we have demonstrated that these solvents can be used as inert reaction media for PVOH modification. Both ionic liquids were found to facilitate the quantitative esterification of PVOH, while only the phosphonium ionic liquid supports the quantitative urethanation of the polymer. In an attempt to tune the surface properties of ionic liquid/polymer solutions, PVOH was also partially esterified with low surface energy substituents. Both surface tension and surface composition of the ionic liquid/polymer solutions can be manipulated by the stoichiometric addition of low surface energy acid chlorides. This work on the modification of PVOH can be directly applied to the modification of polysaccharides such as cellulose which could have important implications from a sustainability and energy standpoint.

Ionic Liquid Fuels for Chemical Propulsion

DTIC Science & Technology

2016-10-31

nucleophilicity in the ionic liquid is critical. Both gas -phase and condensed-phase (CPCM-GIL) density functional theory calculations support the...stability trends in dialkylimidazolium ionic liquids and could be used as a higher accuracy method than the gas -phase DFT approach for predicting thermal...stabilities of ionic liquids in general. One important finding from the comparison of the gas -phase basicities relative to the GIL condensed- phase

Sorption of triclosan onto activated carbon, kaolinite and montmorillonite: effects of pH, ionic strength, and humic acid.

PubMed

Behera, Shishir Kumar; Oh, Seok-Young; Park, Hung-Suck

2010-07-15

Sorption of triclosan on three sorbents, viz., activated carbon, kaolinite and montmorillonite was studied as a function of pH, ionic strength and humic acid (HA) concentration through controlled batch experiments. Triclosan sorption was found to be higher in the acidic pH range, as varying pH showed significant influence on the surface charge of the sorbents and degree of ionization of the sorbate. Sorption capacity of the sorbents increased with an increase in the ionic strength of solution. At low pH (pH 3), the overall increase in triclosan sorption was 1.2, approximately 4 and 3.5 times, respectively for activated carbon, kaolinite and montmorillonite when ionic strength was increased from 1x10(-3) to 5x10(-1) M. Triclosan sorption onto activated carbon decreased from 31.4 to 10.6 mg g(-1) by increasing the HA concentration to 200 mg C L(-1). However, during sorption onto kaolinite and montmorillonite, the effect of HA was very complex probably due to (i) hydrophobicity (log K(ow)=4.76) of triclosan; and (ii) complexation of HA with triclosan. Though triclosan sorption onto activated carbon is higher, the potential of kaolinite and montmorillonite in controlling the transport of triclosan in subsurface environment can still be appreciable. 2010 Elsevier B.V. All rights reserved.

Immobilized chiral tropine ionic liquid on silica gel as adsorbent for separation of metal ions and racemic amino acids.

PubMed

Qian, Guofei; Song, Hang; Yao, Shun

2016-01-15

Tropine-type chiral ionic liquid with proline anion was immobilized on silica gel by chemical modification method for the first time, which was proved by elemental, infrared spectrum and thermogravimetric analysis. Secondly, the performance of this kind of ionic liquid-modified silica gel was investigated in the adsorption of some metal ions, which included Cu(2+), Fe(3+), Mn(2+) and Ni(2+). Then the effects of time, initial concentration and temperature on adsorption for Cu(2+) ions were studied in detail, which was followed by the further research of adsorption kinetics and thermodynamics. The adsorption could be better described by pseudo-second-order kinetics model and that the process was spontaneous, exothermic and entropy decreasing. In the mode of 'reuse after adsorption', the ionic liquid-modified silica gel with saturated adsorption of Cu(2+) was finally used in resolution of racemic amino acids for the first time. The static experiment showed that adsorption rate of two enantiomers was obviously different. Inspired by this, the complex was packed in chromatographic column for the separation of racemic amino acids and d-enantiomers were firstly eluted by water or ethanol. Steric hindrance was found as one of key influencing factors for its effect on the stability of the complex. Copyright © 2015 Elsevier B.V. All rights reserved.

Acid-base titrations of functional groups on the surface of the thermophilic bacterium Anoxybacillus flavithermus: comparing a chemical equilibrium model with ATR-IR spectroscopic data.

PubMed

Heinrich, Hannah T M; Bremer, Phil J; Daughney, Christopher J; McQuillan, A James

2007-02-27

Acid-base functional groups at the surface of Anoxybacillus flavithermus (AF) were assigned from the modeling of batch titration data of bacterial suspensions and compared with those determined from in situ infrared spectroscopic titration analysis. The computer program FITMOD was used to generate a two-site Donnan model (site 1: pKa = 3.26, wet concn = 2.46 x 10(-4) mol g(-1); site 2: pKa = 6.12, wet concn = 6.55 x 10(-5) mol g(-1)), which was able to describe data for whole exponential phase cells from both batch acid-base titrations at 0.01 M ionic strength and electrophoretic mobility measurements over a range of different pH values and ionic strengths. In agreement with information on the composition of bacterial cell walls and a considerable body of modeling literature, site 1 of the model was assigned to carboxyl groups, and site 2 was assigned to amino groups. pH difference IR spectra acquired by in situ attenuated total reflection infrared (ATR-IR) spectroscopy confirmed the presence of carboxyl groups. The spectra appear to show a carboxyl pKa in the 3.3-4.0 range. Further peaks were assigned to phosphodiester groups, which deprotonated at slightly lower pH. The presence of amino groups could not be confirmed or discounted by IR spectroscopy, but a positively charged group corresponding to site 2 was implicated by electrophoretic mobility data. Carboxyl group speciation over a pH range of 2.3-10.3 at two different ionic strengths was further compared to modeling predictions. While model predictions were strongly influenced by the ionic strength change, pH difference IR data showed no significant change. This meant that modeling predictions agreed reasonably well with the IR data for 0.5 M ionic strength but not for 0.01 M ionic strength.

Sorption and complexation of Eu(III) on alumina: effects of pH, ionic strength, humic acid and chelating resin on kinetic dissociation study.

PubMed

Wang, X; Xu, D; Chen, L; Tan, X; Zhou, X; Ren, A; Chen, Ch

2006-04-01

The effects of pH (pH=2-12), ionic strength (0.01-2 mol/l NaNO(3)) and humic acid on the sorption and complexation of Eu(III) on alumina were investigated by using batch techniques. The experiments were carried out at room temperature and under ambient conditions. The results indicate that the sorption of Eu(III) on alumina is strongly influenced by humic acid. The sorption of Eu(III) on alumina is significantly dependent on pH values and independent of ionic strength. The sorption of Eu(III) on alumina may be attributed to surface complexation. The species of Eu(III) on HA-alumina colloids is dominated by both HA and alumina, and the addition sequences of HA or Eu(III) to the ternary system do not influence the sorption of Eu(III) to HA-coated alumina. Kinetic dissociation of Eu(III) from bare and HA-coated alumina was also studied by using the chelating resin. The result was discussed by a pseudo-first-order kinetics model.

Local Dynamics of Acid- and Ion-containing Copolymer Melts

NASA Astrophysics Data System (ADS)

Winey, Karen; Middleton, Robert; Tarver, Jacob; Tyagi, Madhusudan; Soles, Christopher; Frischknecht, Amalie

Interest in acid- and ion-containing polymers arises in part from applications as single-ion conductors for selectively transporting a counter ion for battery applications. Structurally, the low dielectric constant of organic polymers and strong ionic interactions leads to ionic aggregation. Here the polymer backbone motion was investigated through quasi-elastic neutron scattering measurements (QENS) and compared with fully atomistic molecular dynamic simulations of precise poly(ethylene-acrylic acid) copolymers and their ionomers (pxAA-y%Li). The effect of carbon spacer length (x =9, 15, 21) between the acid groups and the degree of neutralization (y) with Li on PE backbone dynamics were considered. Systematic slowing in chain dynamics were observed with increasing neutralization where polymer dynamics appear constrained due to anchoring effects. Simulations provide complementary viewpoints indicating a gradient in chain dynamics as a distance away from acid groups. These results indicate that the addition of pendant acid groups inhibit typical PE backbone motion and the neutralized forms strongly suppress the fraction of mobile PE chain.

Oxidation of alginate and pectate biopolymers by cerium(IV) in perchloric and sulfuric acid solutions: A comparative kinetic and mechanistic study.

PubMed

Fawzy, Ahmed

2016-03-15

The kinetics of oxidation of alginate (Alg) and pectate (Pec) carbohydrate biopolymers was studied by spectrophotometry in aqueous perchloric and sulfuric acid solutions at fixed ionic strengths and temperature. In both acids, the reactions showed a first order dependence on [Ce(IV)], whereas the orders with respect to biopolymer concentrations are less than unity. In perchloric acid, the reactions exhibited less than unit orders with respect to [H(+)] whereas those proceeded in sulfuric acid showed negative fractional-first order dependences on [H(+)]. The effect of ionic strength and dielectric constant was studied. Probable mechanistic schemes for oxidation reactions were proposed. In both acids, the final oxidation products were characterized as mono-keto derivatives of both biopolymers. The activation parameters with respect to the slow step of the mechanisms were computed and discussed. The rate laws were derived and the reaction constants involved in the different steps of the mechanisms were calculated. Copyright © 2015 Elsevier Ltd. All rights reserved.

Sensitivity of the acid-base properties of clays to the methods of preparation and measurement. 2. Evidence from continuous potentiometric titrations.

PubMed

Duc, Myriam; Gaboriaud, Fabien; Thomas, Fabien

2005-09-01

The effects of experimental procedures on the acid-base consumption titration curves of montmorillonite suspension were studied using continuous potentiometric titration. For that purpose, the hysteresis amplitudes between the acid and base branches were found to be useful to systematically evaluate the impacts of storage conditions (wet or dried), the atmosphere in titration reactor, the solid-liquid ratio, the time interval between successive increments, and the ionic strength. In the case of storage conditions, the increase of the hysteresis was significantly higher for longer storage of clay in suspension and drying procedures compared to "fresh" clay suspension. The titration carried out under air demonstrated carbonate contamination that could only be cancelled by performing experiments under inert gas. Interestingly, the increase of the time intervals between successive increments of titrant strongly emphasized the amplitude of hysteresis, which could be correlated with the slow kinetic process specifically observed for acid addition in acid media. Thus, such kinetic behavior is probably associated with dissolution processes of clay particles. However, the resulting curves recorded at different ionic strengths under optimized conditions did not show the common intersection point required to define point of zero charge. Nevertheless, the ionic strength dependence of the point of zero net proton charge suggested that the point of zero charge of sodic montmorillonite could be estimated as lower than 5.

Surface acid-base behaviors of Chinese loess.

PubMed

Chu, Zhaosheng; Liu, Wenxin; Tang, Hongxiao; Qian, Tianwei; Li, Shushen; Li, Zhentang; Wu, Guibin

2002-08-15

Acid-base titration was applied to investigate the surface acid-base properties of a Chinese loess sample at different ionic strengths. The acidimetric supernatant was regarded as the system blank of titration to correct the influence of particle dissolution on the estimation of proton consumption. The titration behavior of the system blank could be described by the hydrolysis of Al3+ and Si(OH)4 in aqueous solution as well as the production of hydroxyaluminosilicates. The formation of Al-Si species on homogeneous surface sites by hydrous aluminum and silicic acid, released from solid substrate during the acidic titration, was considered in the model description of the back-titration procedure. A surface reaction model was suggested as follows: >SOH<-->SO(-)+H+, pK(a)(int)=3.48-3.98;>SOH+Al(3+)+H4SiO4<-->SOAl(OSi(OH)3(+)+2H+, pK(SC)=3.48-4.04. Two simple surface complexation models accounted for the interfacial structure, i.e., the constant capacitance model (CCM) and the diffuse layer model (DLM), and gave a satisfactory description of the experimental data. Considering the effect of ionic strength on the electrostatic profile at the solid-aqueous interface, the DLM was appropriate at the low concentrations (0.01 and 0.005 mol/L) of background electrolyte (NaNO3 in this study), while the CCM was preferable in the case of high ionic strength (0.1 mol/L).

Ionic liquid compatibility in polyethylene oxide/siloxane ion gel membranes

DOE PAGES

Kusuma, Victor A.; Macala, Megan K.; Liu, Jian; ...

2018-10-02

Ion gel films were prepared by incorporating eight commercially available ionic liquids in two different cross-linked polymer matrices to evaluate their phase miscibility, gas permeability and ionic conductivity for potential applications as gas separation membranes and solid electrolyte materials. The ionic liquids cations were 1-ethyl-3-methylimidazolium, 1-ethyl-3-methylpyridinium, 1-butyl-1-methylpyrrolidinium, tributylmethylphosphonium, and butyltrimethylammonium with a common anion (bis(trifluoromethylsulfonyl)imide). In addition, ionic liquids with 1-ethyl-3-methylimidazolium cation with acetate, dicyanamide and tetrafluoroborate counterions were evaluated. The two polymers were cross-linked poly(ethylene oxide) and cross-linked poly(ethylene oxide)/siloxane copolymer. Differential scanning calorimetry, X-ray diffractometry and visual observations were performed to evaluate the ion gels’ miscibility, thermal stabilitymore » and homogeneity. Ionic liquids with the least basic anion (bis(trifluoromethylsulfonyl)imide) and aromatic cations containing acidic proton (e.g. imidazolium and pyridinium) gave the most stable and miscible ion gels. Phase stability was shown to be a function of both ionic liquid content and temperature, with phase separation observed at elevated temperatures. In conclusion, gas permeability testing with carbon dioxide and nitrogen and ionic conductivity measurements confirmed that these ionic liquids increased the gas permeability and ionic conductivity of the polymers.« less

Ionic liquid compatibility in polyethylene oxide/siloxane ion gel membranes

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

Kusuma, Victor A.; Macala, Megan K.; Liu, Jian

Ion gel films were prepared by incorporating eight commercially available ionic liquids in two different cross-linked polymer matrices to evaluate their phase miscibility, gas permeability and ionic conductivity for potential applications as gas separation membranes and solid electrolyte materials. The ionic liquids cations were 1-ethyl-3-methylimidazolium, 1-ethyl-3-methylpyridinium, 1-butyl-1-methylpyrrolidinium, tributylmethylphosphonium, and butyltrimethylammonium with a common anion (bis(trifluoromethylsulfonyl)imide). In addition, ionic liquids with 1-ethyl-3-methylimidazolium cation with acetate, dicyanamide and tetrafluoroborate counterions were evaluated. The two polymers were cross-linked poly(ethylene oxide) and cross-linked poly(ethylene oxide)/siloxane copolymer. Differential scanning calorimetry, X-ray diffractometry and visual observations were performed to evaluate the ion gels’ miscibility, thermal stabilitymore » and homogeneity. Ionic liquids with the least basic anion (bis(trifluoromethylsulfonyl)imide) and aromatic cations containing acidic proton (e.g. imidazolium and pyridinium) gave the most stable and miscible ion gels. Phase stability was shown to be a function of both ionic liquid content and temperature, with phase separation observed at elevated temperatures. In conclusion, gas permeability testing with carbon dioxide and nitrogen and ionic conductivity measurements confirmed that these ionic liquids increased the gas permeability and ionic conductivity of the polymers.« less

First application of supported ionic liquid phase (SILP) catalysis for continuous methanol carbonylation.

PubMed

Riisager, Anders; Jørgensen, Betina; Wasserscheid, Peter; Fehrmann, Rasmus

2006-03-07

A solid, silica-supported ionic liquid phase (SILP) rhodium iodide Monsanto-type catalyst system, [BMIM][Rh(CO)2I2]-[BMIM]I-SiO2, exhibits excellent activity and selectivity towards acetyl products in fixed-bed, continuous gas-phase methanol carbonylation.

Passivation effects on quantum dots prepared by successive ionic layer adsorption and reaction

NASA Astrophysics Data System (ADS)

Dai, Qilin; Maloney, Scott; Chen, Weimin; Poudyal, Uma; Wang, Wenyong

2016-06-01

ZnS is typically used to passivate semiconductor quantum dots (QDs) prepared by the successive ionic layer adsorption and reaction (SILAR) method for solar cell applications, while for colloidal QDs, organic ligands are usually used for this passivation purpose. In this study we utilized oleylamine and oleic acid ligands, besides ZnS, to passivate QDs prepared by the SILAR approach, and investigated their effects on the incident photon-to-current efficiency (IPCE) performance of the solar cells. It was observed that oleylamine passivation decreased device performance, while oleic acid passivation improved the IPCE of the cells. Redshift of the IPCE onset wavelength was also observed after oleic acid coating, which was attributed to the delocalization of excitons in the CdS QDs.

Regioselctive Thiocyanation of Aromatic and Heteroaromatic Compounds Using a Novel Bronsted Acidic Ionic Liquid.

PubMed

Rezayati, Sobhan; Sheikholeslami-Farahani, Fatemeh; Hossaini, Zinatossadat; Hajinasiri, Rahimeh; Abad, Saeid Afshari Sharif

2016-01-01

A convenient procedure for the preparation of 1-(1-Propylsulfonic)-3- methylimidazolium thiocyanate as a novel Brønsted acidic ionic liquid thiocyanation agent and highly efficient heterogeneous catalytic is described. This catalyst is used in regioselective thiocyanation of indoles, anilines, pyrroles and their derivatives (aromatic and heteroaromatic organic compounds) in the presence of H2O2 as a mild and oxidant in EtOH:H2O (1:1 v/v). These reactions are performed under mild and simple conditions and give regioselective products in high yields and short reaction time.

Enantioselective Organocatalytic Aminomethylation of Aldehydes: A Role for Ionic Interactions and Efficient Access to β2-Amino Acids

PubMed Central

Chi, Yonggui; Gellman, Samuel H.

2009-01-01

Organocatalytic Mannich addition of aldehydes to a formaldehyde-derived iminium species catalyzed by proline-derived chiral pyrrolidines provides β-amino aldehydes with ≥ 90% ee. Mechanistic analysis of the proline-catalyzed reactions suggests that non-hydrogen-bonded ionic interactions at the Mannich reaction transition state can influence stereochemical outcome. The β-amino aldehydes from our process bear a substituent adjacent to the carbonyl and can be efficiently converted to protected β2-amino acids, which are important building blocks for β-peptide foldamers that display useful biological activities. PMID:16719457

Stability and activity of lysozyme in stoichiometric and non-stoichiometric protic ionic liquid (PIL)-water systems

NASA Astrophysics Data System (ADS)

Wijaya, Emmy C.; Separovic, Frances; Drummond, Calum J.; Greaves, Tamar L.

2018-05-01

There has been a substantial increase in enzyme applications within the biochemical and pharmaceutical industries, for example, as industrial biocatalysts. However, enzymes have narrow marginal stability which makes them prone to become inactive and/or denature with a slight change in the solvent environment. Typically industrial applications require harsher solvent environments than enzyme native environments, and hence there is a need to understand solvent-protein interactions in order to develop strategies to maintain, or enhance, the enzymatic activity under industrially relevant solvent conditions. Previously we have shown that protic ionic liquids (PILs) with water can have a stabilising effect on lysozyme, with a large variation dependent on which PIL ions are present, and the water concentration [E. C. Wijaya et al., Phys. Chem. Chem. Phys. 18(37), 25926-25936 (2016)]. Here we extend on this work using non-stoichiometric aqueous PIL solvents to investigate, and isolate, the role of pH and ionicity on enzymes. We have used the PILs ethylammonium nitrate (EAN) and ethanolammonium formate (EOAF) since our previous work has identified these as good solvents for lysozyme. Solvent libraries were made from these two PILs with an additional precursor acid or base to modify the acidity/basicity of the neutral stoichiometric PIL, and with water added, to have solutions with 4-17 mol. % of the PIL ions in water. Molar ratios of base:acid were varied between 1:1.05 and 2:1 for EAN and 1:1.25 and 2:1 for EOAF, which enabled from highly basic to highly acidic solutions to be obtained. This was to modify the acidity/basicity of the neutral stoichiometric PILs, without the addition of buffers. The structure and stability of hen egg white lysozyme (HEWL) were explored under these solvent conditions using synchrotron small angle X-ray scattering (SAXS), Fourier transform infrared (FTIR), and activity assays. The radius of gyration and Kratky plots obtained from the SAXS data showed little change with varying ionicity or acid:base ratio. FTIR showed that α-helix was maintained in all, except for the most acidic solvent conditions. The activity data show that HEWL was active between pH 0 and 11 for the EA:N-water system and pH 4.4 and 11 for the EOA:F-water system. This work indicates that ionic liquids have the potential to enable enzymes to maintain activity across a broader range of solvent conditions.

Gas chromatographic analysis of fatty acid methyl esters of milk fat by an ionic liquid derived from L-phenylalanine as the stationary phase.

PubMed

Mendoza, Laura González; González-Álvarez, Jaime; Gonzalo, Carla Fernández; Arias-Abrodo, Pilar; Altava, Belén; Luis, Santiago V; Burguete, Maria Isabel; Gutiérrez-Álvarez, María Dolores

2015-10-01

A Gas Chromatography (GC) method has been developed for the separation and characterization of the different fatty acids in anhydrous milk fat (AMF) by means of an ionic liquid stationary phase, characterized by a monocationic imidazolium salt derived from L-phenylalanine. The inner surface of a fused silica capillary column was modified using this ionic liquid functionality and 3-aminopropyldiethoxymethyl silane. This coated GC column, which exhibited good thermal stability (270°C) and good efficiency (2700 plates/m), has been characterized using the Abraham solvation parameter model. The intra-day and inter-day precision of the method have been evaluated, obtaining relative standard deviations (RSD) from 0.99% to 4.0% and from 2.8% to 9.2%, respectively. Furthermore, recoveries from 90% and 99% have been achieved. Copyright © 2015 Elsevier B.V. All rights reserved.

SORPTION OF CU AND ZN TO KAOLINITE AND IRON OXIDE: EFFECTS OF HUMIC ACID AND IONIC STRENGTH AND IMPLICATIONS FOR STORMWATER RUNOFF

EPA Science Inventory

Heavy metals are common pollutants in wet weather flows and urban waterways. Changes in ionic strength, whether from mixing with saline waters, road salt, or from the large osmotic adjustment needed for the Microtox toxicity assay, affect the aqueous chemistry of stormwater runof...

Development of Monopole Interaction Models for Ionic Compounds. Part I: Estimation of Aqueous Henry’s Law Constants for Ions and Gas Phase pKa Values for Acidic Compounds

EPA Science Inventory

The SPARC (SPARC Performs Automated Reasoning in Chemistry) physicochemical mechanistic models for neutral compounds have been extended to estimate Henry’s Law Constant (HLC) for charged species by incorporating ionic electrostatic interaction models. Combinations of absolute aq...

INORGANIC AND ORGANIC ONIUM SALTS

DTIC Science & Technology

The nitrosonium NO ion absorbs in the infrared between 1/2400 and 1/ 2150 cm. Salts of complex fluoro-acids absorb at higher frequencies than salts...halide adducts generally contain nitrosonium ions . Hexaphenylditin does not undergo marked heterolytic dissociation in nitromethane solution...influencing the covalent-ionic equilibrium are discussed. Infrared spectrum nitrosonium ion ; ionic character in lattice and position nitrosonium ion absorption

Ionic Liquid-Based Optical and Electrochemical Carbon Dioxide Sensors.

PubMed

Behera, Kamalakanta; Pandey, Shubha; Kadyan, Anu; Pandey, Siddharth

2015-12-04

Due to their unusual physicochemical properties (e.g., high thermal stability, low volatility, high intrinsic conductivity, wide electrochemical windows and good solvating ability), ionic liquids have shown immense application potential in many research areas. Applications of ionic liquid in developing various sensors, especially for the sensing of biomolecules, such as nucleic acids, proteins and enzymes, gas sensing and sensing of various important ions, among other chemosensing platforms, are currently being explored by researchers worldwide. The use of ionic liquids for the detection of carbon dioxide (CO₂) gas is currently a major topic of research due to the associated importance of this gas with daily human life. This review focuses on the application of ionic liquids in optical and electrochemical CO₂ sensors. The design, mechanism, sensitivity and detection limit of each type of sensor are highlighted in this review.

Ionic Liquid-Based Optical and Electrochemical Carbon Dioxide Sensors

PubMed Central

Behera, Kamalakanta; Pandey, Shubha; Kadyan, Anu; Pandey, Siddharth

2015-01-01

Due to their unusual physicochemical properties (e.g., high thermal stability, low volatility, high intrinsic conductivity, wide electrochemical windows and good solvating ability), ionic liquids have shown immense application potential in many research areas. Applications of ionic liquid in developing various sensors, especially for the sensing of biomolecules, such as nucleic acids, proteins and enzymes, gas sensing and sensing of various important ions, among other chemosensing platforms, are currently being explored by researchers worldwide. The use of ionic liquids for the detection of carbon dioxide (CO2) gas is currently a major topic of research due to the associated importance of this gas with daily human life. This review focuses on the application of ionic liquids in optical and electrochemical CO2 sensors. The design, mechanism, sensitivity and detection limit of each type of sensor are highlighted in this review. PMID:26690155

Selective Extraction of Uranium from Liquid or Supercritical Carbon Dioxide

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

Farawila, Anne F.; O'Hara, Matthew J.; Wai, Chien M.

2012-07-31

Current liquid-liquid extraction processes used in recycling irradiated nuclear fuel rely on (1) strong nitric acid to dissolve uranium oxide fuel, and (2) the use of aliphatic hydrocarbons as a diluent in formulating the solvent used to extract uranium. The nitric acid dissolution process is not selective. It dissolves virtually the entire fuel meat which complicates the uranium extraction process. In addition, a solvent washing process is used to remove TBP degradation products, which adds complexity to the recycling plant and increases the overall plant footprint and cost. A liquid or supercritical carbon dioxide (l/sc -CO2) system was designed tomore » mitigate these problems. Indeed, TBP nitric acid complexes are highly soluble in l/sc -CO2 and are capable of extracting uranium directly from UO2, UO3 and U3O8 powders. This eliminates the need for total acid dissolution of the irradiated fuel. Furthermore, since CO2 is easily recycled by evaporation at room temperature and pressure, it eliminates the complex solvent washing process. In this report, we demonstrate: (1) A reprocessing scheme starting with the selective extraction of uranium from solid uranium oxides into a TBP-HNO3 loaded Sc-CO2 phase, (2) Back extraction of uranium into an aqueous phase, and (3) Conversion of recovered purified uranium into uranium oxide. The purified uranium product from step 3 can be disposed of as low level waste, or mixed with enriched uranium for use in a reactor for another fuel cycle. After an introduction on the concept and properties of supercritical fluids, we first report the characterization of the different oxides used for this project. Our extraction system and our online monitoring capability using UV-Vis absorbance spectroscopy directly in sc-CO2 is then presented. Next, the uranium extraction efficiencies and kinetics is demonstrated for different oxides and under different physical and chemical conditions: l/sc -CO2 pressure and temperature, TBP/HNO3 complex used, reductant or complexant used for selectivity, and ionic liquids used as supportive media. To complete the extraction and recovery cycle, we then demonstrate uranium back extraction from the TBP loaded sc-CO2 phase into an aqueous phase and the characterization of the uranium complex formed at the end of this process. Another aspect of this project was to limit proliferation risks by either co-extracting uranium and plutonium, or by leaving plutonium behind by selectively extracting uranium. We report that the former is easily achieved, since plutonium is in the tetravalent or hexavalent oxidation state in the oxidizing environment created by the TBP-nitric acid complex, and is therefore co-extracted. The latter is more challenging, as a reductant or complexant to plutonium has to be used to selectively extract uranium. After undertaking experiments on different reducing or complexing systems (e.g., AcetoHydroxamic Acid (AHA), Fe(II), ascorbic acid), oxalic acid was chosen as it can complex tetravalent actinides (Pu, Np, Th) in the aqueous phase while allowing the extraction of hexavalent uranium in the sc-CO2 phase. Finally, we show results using an alternative media to commonly used aqueous phases: ionic liquids. We show the dissolution of uranium in ionic liquids and its extraction using sc-CO2 with and without the presence of AHA. The possible separation of trivalent actinides from uranium is also demonstrated in ionic liquids using neodymium as a surrogate and diglycolamides as the extractant.« less

[Effects of simulated acid rain on respiration rate of cropland system with different soil pH].

PubMed

Zhu, Xue-zhu; Zhang, Gao-chuan; Li, Hui

2009-10-15

To evaluate the effects of acid rain on the respiration rate of cropland system, an outdoor pot experiment was conducted with paddy soils of pH 5.48 (S1), pH 6.70 (S1) and pH 8.18 (S3) during the 2005-2007 wheat-growing seasons. The cropland system was exposed to acid rain by spraying the wheat foliage and irrigating the soil with simulated rainwater of T1 (pH 6.0), T2 (pH 6.0, ionic concentration was twice as rainwater T1), and T3 (pH 4.4, ionic concentration was twice as rainwater T1), respectively. The static opaque chamber-gas chromatograph method was used to measure CO2 fluxes from cropland system. The results showed that acid rain affected the respiration rate of cropland system through crop plant, and the cropland system could adapt to acid rain. Acid rainwater significantly increased the average respiration rate in alkaline soil (S3) cropland system, while it had no significant effects on the average respiration rate in neutral soil (S2) and acidic soil (S1) cropland systems. During 2005-2006, after the alkaline soil cropland system was treated with rainwater T3, the average respiration rate was 23.6% and 27.6% higher than that of alkaline soil cropland system treated with rainwater T1 and T2, respectively. During March to April, the respiration rate was enhanced with the increase of rainwater ionic concentration, while it was dropped with the decrease of rainwater pH value in acidic soil cropland system. It was demonstrated that soil pH and crop plant played important roles on the respiration rate of cropland system.

DFT study of the energetic and noncovalent interactions between imidazolium ionic liquids and hydrofluoric acid.

PubMed

Velarde, Marco V; Gallo, Marco; Alonso, P A; Miranda, A D; Dominguez, J M

2015-04-16

In this work, we evaluated the energetic interactions between imidazolium ionic liquids (ILs) and hydrofluoric acid, as well as the cation-anion interactions in ILs. We used DFT calculations that include dispersion corrections employing the PBE and M06 functionals. We tested 22 ILs, including [C4MIM][PF6], [C4MIM][NTf2], and [C4MIM][CH3COO], obtaining interaction energies in the range of -27 to -13 kcal/mol with the PBE functional. The NCI (noncovalent interaction) index developed by Yang and collaborators ( J. Am. Chem. Soc. 2010 , 132 , 6498 - 6506 ; J. Chem. Theory Comput. 2011 , 7 , 625 - 632 ) also was used for mapping the key noncovalent interactions (hydrogen bonds, van der Waals, and steric repulsions) between the anions and cations of ILs and also for interactions of ILs with hydrofluoric acid (HF). The results obtained show that the anions have a stronger effect with respect to cations in their capacity for interacting with hydrofluoric acid, and the strongest interaction energies occur in systems where the key noncovalent interactions are mainly hydrogen bonds. The [C4MIM][PF6], [C4MIM][NTf2], and [C4MIM][BF4] ionic liquids displayed the weakest cation-anion interactions.

Self-Supporting, Hydrophobic, Ionic Liquid-Based Reference Electrodes Prepared by Polymerization-Induced Microphase Separation

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

Chopade, Sujay A.; Anderson, Evan L.; Schmidt, Peter W.

Interfaces of ionic liquids and aqueous solutions exhibit stable electrical potentials over a wide range of aqueous electrolyte concentrations. This makes ionic liquids suitable as bridge materials that separate in electroanalytical measurements the reference electrode from samples with low and/or unknown ionic strengths. However, methods for the preparation of ionic liquid-based reference electrodes have not been explored widely. We have designed a convenient and reliable synthesis of ionic liquid-based reference electrodes by polymerization-induced microphase separation. This technique allows for a facile, single-pot synthesis of ready-to-use reference electrodes that incorporate ion conducting nanochannels filled with either 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide or 1-dodecyl-3-methylimidazolium bis(trifluoromethylmore » sulfonyl)imide as ionic liquid, supported by a mechanically robust cross-linked polystyrene phase. This synthesis procedure allows for the straightforward design of various reference electrode geometries. These reference electrodes exhibit a low resistance as well as good reference potential stability and reproducibility when immersed into aqueous solutions varying from deionized, purified water to 100 mM KCl, while requiring no correction for liquid junction potentials.« less

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.

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

An adaptive self-healing ionic liquid nanocomposite membrane for olefin-paraffin separations.

PubMed

Pitsch, Fee; Krull, Florian F; Agel, Friederike; Schulz, Peter; Wasserscheid, Peter; Melin, Thomas; Wessling, Matthias

2012-08-16

An adaptive self-healing ionic liquid nanocomposite membrane comprising a multi-layer support structure hosting the ionic salt [Ag](+) [Tf(2) N](-) is used for the separation of the olefin propylene and the paraffin propane. The ionic salt renders liquid like upon complexation with propylene, resulting in facilitated transport of propylene over propane at benchmark-setting selectivity and permeance levels. The contacting with acetylene causes the ionic salt to liquefy without showing evidence of forming explosive silver acetylide. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Recent developments in biocatalysis in multiphasic ionic liquid reaction systems.

PubMed

Meyer, Lars-Erik; von Langermann, Jan; Kragl, Udo

2018-06-01

Ionic liquids are well known and frequently used 'designer solvents' for biocatalytic reactions. This review highlights recent achievements in the field of multiphasic ionic liquid-based reaction concepts. It covers classical biphasic systems including supported ionic liquid phases, thermo-regulated multi-component solvent systems (TMS) and polymerized ionic liquids. These powerful concepts combine unique reaction conditions with a high potential for future applications on a laboratory and industrial scale. The presence of a multiphasic system simplifies downstream processing due to the distribution of the catalyst and reactants in different phases.

Electrochemical Polishing Applications and EIS of a Vitamin B{sub 4}-Based Ionic Liquid

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

Wixtrom, Alex I.; Buhler, Jessica E.; Reece, Charles E.

2013-01-01

Modern particle accelerators require minimal interior surface roughness for Niobium superconducting radio frequency (SRF) cavities. Polishing of the Nb is currently achieved via electrochemical polishing with concentrated mixtures of sulfuric and hydrofluoric acids. This acid-based approach is effective at reducing the surface roughness to acceptable levels for SRF use, but due to acid-related hazards and extra costs (including safe disposal of used polishing solutions), an acid-free method would be preferable. This study focuses on an alternative electrochemical polishing method for Nb, using a novel ionic liquid solution containing choline chloride, also known as Vitamin B{sub 4} (VB{sub 4}). Potentiostatic electrochemicalmore » impedance spectroscopy (EIS) was also performed on the VB4-based system. Nb polished using the VB4-based method was found to have a final surface roughness comparable to that achieved via the acid-based method, as assessed by atomic force microscopy (AFM). These findings indicate that acid-free VB{sub 4}-based electrochemical polishing of Nb represents a promising replacement for acid-based methods of SRF cavity preparation.« less

Physicochemical properties of betaine monohydrate-carboxylic acid mixtures

NASA Astrophysics Data System (ADS)

Zahrina, I.; Nasikin, M.; Mulia, K.

2018-05-01

Green solvents are widely used to minimize environmental problems associated with the use of volatile organic solvents in many industries. DES are new green solvents in recent. The physicochemical properties of DES can be varied by properly combining of salts with different hydrogen bond donors. The objective of this work is to investigate the effect of varying molar ratios on the physicochemical properties of betaine monohydrate-carboxylic acid (i.e,. propionic or acetic acid) mixtures. Properties of mixtures were measured at 40°C. The viscosity, polarity scale (ENR), density, pH, and water content tend to decrease with the decrease in a molar ratio of betaine monohydrate to acid. Conversely, the ionic conductivity was increased. The physicochemical properties of these mixtures depend on the hydrogen bonding interactions between betaine, water and acid molecules. Betaine monohydratecarboxylic acid mixtures have wide range of polarity, low viscosity, high ionic conductivity, and density higher than 1 g·cm-3 that make them fit for numerous various applications. Additionally, due to these mixtures have acidic pH, it should be properly selected of metal type to minimize corrosion problems in industrial application.

Molecular dynamics simulation studies of the interactions between ionic liquids and amino acids in aqueous solution.

PubMed

Tomé, Luciana I N; Jorge, Miguel; Gomes, José R B; Coutinho, João A P

2012-02-16

Although the understanding of the influence of ionic liquids (ILs) on the solubility behavior of biomolecules in aqueous solutions is relevant for the design and optimization of novel biotechnological processes, the underlying molecular-level mechanisms are not yet consensual or clearly elucidated. In order to contribute to the understanding of the molecular interactions established between amino acids and ILs in aqueous media, classical molecular dynamics (MD) simulations were performed for aqueous solutions of five amino acids with different structural characteristics (glycine, alanine, valine, isoleucine, and glutamic acid) in the presence of 1-butyl-3-methylimidazolium bis(trifluoromethyl)sulfonyl imide. The results from MD simulations enable to relate the properties of the amino acids, namely their hydrophobicity, to the type and strength of their interactions with ILs in aqueous solutions and provide an explanation for the direction and magnitude of the solubility phenomena observed in [IL + amino acid + water] systems by a mechanism governed by a balance between competitive interactions of the IL cation, IL anion, and water with the amino acids.

Transformation of the Ionic X-Ray Contrast Agent Diatrizoate and Related Triiodinated Benzoates by Trametes versicolor

PubMed Central

Rode, Ulrike; Müller, Rudolf

1998-01-01

Iodinated X-ray contrast agents are considered to be nondegradable by microorganisms. The decomposition of the ionic X-ray contrast agents Diatrizoate (3,5-di(acetamido)-2,4,6-triiodobenzoic acid) and Iodipamide (3,3′-adipoyl-diimino-di(2,4,6-triiodobenzoic acid) and related triiodinated benzoates (Acetrizoate [3-acetylamino-2,4,6-triiodobenzoic acid] and Aminotrizoate [3-amino-2,4,6-triiodobenzoic acid]) by Trametes versicolor has been investigated. The fungus was able to transform all tested triiodinated benzoates cometabolically. During transformation of these compounds, iodide was released, but deiodination was not complete. T. versicolor liberated traces of 14CO2 from uniformly ring-14C-labeled Diatrizoate (3,5-di(acetamido)-2,4,6-triiodobenzoate). Various extracellular metabolites were detected during transformation of the different substances. In the transformation of Diatrizoate, the three main metabolites were identified as 3,5-di(acetamido)-2,6-diiodobenzoic acid, 3,5-di(acetamido)-2,4-diiodobenzoic acid, and 3,5-di(acetamido)-2-iodobenzoic acid, suggesting reductive deiodinations in steps as initial transformation steps. PMID:9687487

Volatile times for the very first ionic liquid: understanding the vapor pressures and enthalpies of vaporization of ethylammonium nitrate.

PubMed

Emel'yanenko, Vladimir N; Boeck, Gisela; Verevkin, Sergey P; Ludwig, Ralf

2014-09-08

A hundred years ago, Paul Walden studied ethyl ammonium nitrate (EAN), which became the first widely known ionic liquid. Although EAN has been investigated extensively, some important issues still have not been addressed; they are now tackled in this communication. By combining experimental thermogravimetric analysis with time of flight mass spectrometry (TGA-ToF-MS) and transpiration method with theoretical methods, we clarify the volatilisation of EAN from ambient to elevated temperatures. It was observed that up to 419 K, EAN evaporates as contact-ion pairs leading to very low vapour pressures of a few Pascal. Starting from 419 K, the decomposition to nitric acid and ethylamine becomes more thermodynamically favourable than proton transfer. This finding was supported by DFT calculations, which provide the free energies of all possible gas-phase species, and show that neutral molecules dominate over ion pairs above 500 K, an observation that is in nearly prefect agreement with the experimental boiling point of 513 K. This result is crucial for the ongoing practical applications of protic ionic liquids such as electrolytes for batteries and fuel cells because, in contrast to high-boiling conventional solvents, EAN exhibits no significant vapour pressure below 419 K and this property fulfils the requirements for the thermal behaviour of safe electrolytes. Overall, EAN shows the same barely measurable vapour pressures as typical aprotic ionic liquids at temperatures only 70 K lower. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Are clinical findings of systemic titanium dispersion following implantation explained by available in vitro evidence? An evidence-based analysis.

PubMed

Curtin, Justin Paul; Wang, Minji

2017-08-01

Although the presence of titanium wear particles released into tissues is known to induce local inflammation following the therapeutic implantation of titanium devices into humans, the role that titanium ions play in adverse tissue responses has received little attention. Support that ongoing titanium ion release occurs is evidenced by the presence of ionic titanium bound to transferrin in blood, and ongoing excretion in the urine of patients with titanium devices. However, as reports documenting the presence of titanium within tissues do not distinguish between particulate and ionic forms due to technical challenges, the degree to which ionic titanium is released into tissues is unknown. To determine the potential for titanium ion release into tissues, this study evaluates available in vitro evidence relating to the release of ionic titanium under physiological conditions. This is a systematic literature review of studies reporting titanium ion release into solutions from titanium devices under conditions replicating the interstitial pH and constituents. Inclusion and exclusion criteria were defined. Of 452 articles identified, titanium ions were reported in nine media relevant to human biology in seventeen studies. Only one study, using human serum replicated both physiological pH and the concentration of constituents while reporting the presence of titanium ions. While there is insufficient information to explain the factors that contribute to the presence of titanium ions in serum of humans implanted with titanium devices, currently available information suggests that areas of future inquiry include the role of transferrin and organic acids.

Gas chromatography on wall-coated open-tubular columns with ionic liquid stationary phases.

PubMed

Poole, Colin F; Lenca, Nicole

2014-08-29

Ionic liquids have moved from novel to practical stationary phases for gas chromatography with an increasing portfolio of applications. Ionic liquids complement conventional stationary phases because of a combination of thermophysical and solvation properties that only exist for ionic solvents. Their high thermal stability and low vapor pressure makes them suitable as polar stationary phases for separations requiring high temperatures. Ionic liquids are good solvents and can be used to expand the chemical space for separations. They are the only stationary phases with significant hydrogen-bond acidity in common use; they extend the hydrogen-bond basicity of conventional stationary phases; they are as dipolar/polarizable as the most polar conventional stationary phases; and some ionic liquids are significantly less cohesive than conventional polar stationary phases. Problems in column coating techniques and related low column performance, column activity, and stationary phase reactivity require further exploration as the reasons for these features are poorly understood at present. Copyright © 2014 Elsevier B.V. All rights reserved.

Preparation and characterization of nonaqueous proton-conducting membranes with protic ionic liquids.

PubMed

Lu, Fei; Gao, Xinpei; Yan, Xiaojun; Gao, Hejun; Shi, Lijuan; Jia, Han; Zheng, Liqiang

2013-08-14

Hybrid Nafion membranes were successfully fabricated by incorporating with protic imidazolium ionic liquids 1-(2-aminoethyl)-3-methylimidazolium chloride ([MimAE]Cl), 1-(2-hydroxylethyl)-3-methylimidazolium chloride ([MimHE]Cl), and 1-carboxylmethyl-3-methylimidazolium chloride ([MimCM]Cl) for high-temperature fuel cells. The composite membranes were characterized by impedance spectroscopy, small-angle X-ray scattering (SAXS), scanning electronic microscopy (SEM), and thermogravimetric analysis (TGA). The incorporated protic ionic liquids enhance the doping of phosphoric acid (PA) and result in a relatively high ionic conductivity. The Nafion/10 wt % [MimAE]Cl/PA composite membrane exhibits an ionic conductivity of 6.0 mS/cm at 130 °C without humidification. [MimAE]Cl can swell the Nafion matrix more homogeneously than [MimHE]Cl or [MimCM]Cl, which results in a better ionic conductivity. It is notable that the composite Nafion/IL/PA membranes have a better thermal stability than the pristine Nafion membranes.

A New Green Ionic Liquid-Based Corrosion Inhibitor for Steel in Acidic Environments.

PubMed

Atta, Ayman M; El-Mahdy, Gamal A; Al-Lohedan, Hamad A; Ezzat, Abdel Rahman O

2015-06-17

This work examines the use of new hydrophobic ionic liquid derivatives, namely octadecylammonium tosylate (ODA-TS) and oleylammonium tosylate (OA-TS) for corrosion protection of steel in 1 M hydrochloric acid solution. Their chemical structures were determined from NMR analyses. The surface activity characteristics of the prepared ODA-TS and OA-TS were evaluated from conductance, surface tension and contact angle measurements. The data indicate the presence of a double bond in the chemical structure of OA-TS modified its surface activity parameters. Potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) measurements, scanning electron microscope (SEM), Energy dispersive X-rays (EDX) analysis and contact angle measurements were utilized to investigate the corrosion protection performance of ODA-TS and OA-TS on steel in acidic solution. The OA-TS and ODA-TS compounds showed good protection performance in acidic chloride solution due to formation of an inhibitive film on the steel surface.

Poly(ionic liquid) based chemosensors for detection of basic amino acids in aqueous medium

NASA Astrophysics Data System (ADS)

Li, Xinjuan; Wang, Kai; Ma, Nana; Jia, Xianbin

2017-09-01

Naked-eye detection of amino acids in water is of great significance in the field of bio-analytical applications. Herein, polymerized ionic liquids (PILs) with controlled chain length structures were synthesized via reversible addition-fragmentation chain-transfer (RAFT) polymerization and post-quaternization approach. The amino acids recognition performance of PILs with different alkyl chain lengths and molecular weights was evaluated by naked-eye color change and ultraviolet-visible (UV-vis) spectral studies. These PILs were successfully used for highly sensitive and selective detection of Arg, Lys and His in water. The recognition performance was improved effectively with increased molecular weight of PILs. The biosensitivity of the PILs in water was strongly dependent on their aggregation effect and polarization effect. Highly sensitive and selective detection of amino acids was successfully accomplished by introducing positively charged pyridinium moieties and controlled RAFT radical polymerization.

Hollow Fiber Supported Ionic Liquids Liquid-Phase Micro-extraction Followed by High-Performance Liquid Chromatography for the Determination of Polycyclic Aromatic Hydrocarbons in Milk Samples.

PubMed

Wang, Meng; Cheng, Chunsheng; Liu, Chunbo; Yang, Yaling

2018-01-01

A rapid, simple, reliable and efficient hollow fiber supported ionic liquids liquid-phase micro-extraction method (IL-HF-LPME) followed by high-performance liquid chromatography was successfully applied to the determination of four kinds of polycyclic aromatic hydrocarbons (PAHs) in milk samples. In the IL-HF-LPME method, a mixture of [OMIM]PF6 and lauric acid, in a ratio of 3:1, was immobilized in the pores of a polypropylene hollow fiber used as extraction solvent. A series of essential parameters influencing the extraction efficiency were investigated and optimized. Under the optimal conditions, the extraction equilibrium is achieved within 3 min, the good linearity was >0.9990, the limits of detection varied from 0.14 to 0.71 ng/mL, the limit of quantification values were between 0.4 and 1.8 ng/mL, and the relative standard deviations were in the range of 1.24-3.27% (n = 5). The proposed method was applied to analyze four PAHs in milk samples and recoveries were between 93.6 and 102.8%. © The Author 2017. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Ionic Liquids in Selective Oxidation: Catalysts and Solvents.

PubMed

Dai, Chengna; Zhang, Jie; Huang, Chongpin; Lei, Zhigang

2017-05-24

Selective oxidation has an important role in environmental and green chemistry (e.g., oxidative desulfurization of fuels and oxidative removal of mercury) as well as chemicals and intermediates chemistry to obtain high-value-added special products (e.g., organic sulfoxides and sulfones, aldehydes, ketones, carboxylic acids, epoxides, esters, and lactones). Due to their unique physical properties such as the nonvolatility, thermal stability, nonexplosion, high polarity, and temperature-dependent miscibility with water, ionic liquids (ILs) have attracted considerable attention as reaction solvents and media for selective oxidations and are considered as green alternatives to volatile organic solvents. Moreover, for easy separation and recyclable utilization, IL catalysts have attracted unprecedented attention as "biphasic catalyst" or "immobilized catalyst" by immobilizing metal- or nonmetal-containing ILs onto mineral or polymer supports to combine the unique properties of ILs (chemical and thermal stability, capacity for extraction of polar substrates and reaction products) with the extended surface of the supports. This review highlights the most recent outcomes on ILs in several important typical oxidation reactions. The contents are arranged in the series of oxidation of sulfides, oxidation of alcohols, epoxidation of alkenes, Baeyer-Villiger oxidation reaction, oxidation of alkanes, and oxidation of other compounds step by step involving ILs as solvents, catalysts, reagents, or their combinations.

Electrostatic Steering Accelerates C3d:CR2 Association.

PubMed

Mohan, Rohith R; Huber, Gary A; Morikis, Dimitrios

2016-08-25

Electrostatic effects are ubiquitous in protein interactions and are found to be pervasive in the complement system as well. The interaction between complement fragment C3d and complement receptor 2 (CR2) has evolved to become a link between innate and adaptive immunity. Electrostatic interactions have been suggested to be the driving factor for the association of the C3d:CR2 complex. In this study, we investigate the effects of ionic strength and mutagenesis on the association of C3d:CR2 through Brownian dynamics simulations. We demonstrate that the formation of the C3d:CR2 complex is ionic strength-dependent, suggesting the presence of long-range electrostatic steering that accelerates the complex formation. Electrostatic steering occurs through the interaction of an acidic surface patch in C3d and the positively charged CR2 and is supported by the effects of mutations within the acidic patch of C3d that slow or diminish association. Our data are in agreement with previous experimental mutagenesis and binding studies and computational studies. Although the C3d acidic patch may be locally destabilizing because of unfavorable Coulombic interactions of like charges, it contributes to the acceleration of association. Therefore, acceleration of function through electrostatic steering takes precedence to stability. The site of interaction between C3d and CR2 has been the target for delivery of CR2-bound nanoparticle, antibody, and small molecule biomarkers, as well as potential therapeutics. A detailed knowledge of the physicochemical basis of C3d:CR2 association may be necessary to accelerate biomarker and drug discovery efforts.

[Molecular Dynamics of N- and C-terminal Interactions during Autoinhibition and Activation of Formin mDial].

PubMed

Orshanskiy, I A; Popinako, A V; Volokh, O I; Shaitan, K V; Sokolova, O S

2015-01-01

With the method of molecular dynamics, pairs of amino acid residues have been identified on the surface of the interacting formin mDial domains: DID-DAD, which are responsible for the autoinhibition of formin, and the GTPase Rho-DID domain, and control activation. It was found that the most stable interactions are ionic interactions between Glu178 residue and Arg248 residue, as well as hydrophobic interactions between Thr175 and Phe247. The strongest interactions proved to be between the DID domain with Rho-GTPase. These interactions are mediated by specific triple ionic interactions between positively charged amino acid in Rho, and a triplet of amino acids in DID, consisting of two negatively charged amino acids, separated by one uncharged. Binding sites for Rho-GTPase and DAD partially overlap, but various amino acids on the DID participate in interactions with different domains. We discuss the possible conformational changes in formin domains during activation and inactivation.

Predominance Diagrams, a Useful Tool for the Correlation of the Precipitation-Solubility Equilibrium with Other Ionic Equilibria

ERIC Educational Resources Information Center

Pereira, Constantino Fernandez; Alcalde, Manuel; Villegas, Rosario; Vale, Jose

2007-01-01

The four types of ionic equilibria--acid-base, redox, precipitation, and complexation--have certain similarities, which has led some authors to develop a unified treatment of them. These authors have highlighted the common aspects and tried to find a systemization of the equilibria that would facilitate learning them. In this unified treatment,…

Development of a novel naphthoic acid ionic liquid and its application in "no-organic solvent microextraction" for determination of triclosan and methyltriclosan in human fluids and the method optimization by central composite design.

PubMed

Wang, Hui; Gao, Jiajia; Yu, Nana; Qu, Jingang; Fang, Fang; Wang, Huili; Wang, Mei; Wang, Xuedong

2016-07-01

In traditional ionic liquids (ILs)-based microextraction, the hydrophobic and hydrophilic ILs are often used as extractant and disperser, respectively. However, the functional effects of ILs are not utilized in microextraction procedures. Herein, we introduced 1-naphthoic acid into imidazolium ring to synthesize a novel ionic liquid 1-butyl-3-methylimidazolium naphthoic acid salt ([C4MIM][NPA]), and its structure was characterized by IR, (1)H NMR and MS. On the basis of its acidic property and lower solubility than common [CnMIM][BF4], it was used as a mixing dispersive solvent with [C4MIM][BF4] in "functionalized ionic liquid-based no organic solvent microextraction (FIL-NOSM)". Utilization of [C4MIM][NPA] in FIL-NOSM procedures has two obvious advantages: (1) it promoted the non-polar environment, increased volume of the sedimented phase, and thus could enhance the extraction recoveries of triclosan (TCS) and methyltriclosan (MTCS) by more than 10%; and (2) because of the acidic property, it can act as a pH modifier, avoiding extra pH adjustment step. By combining single factor optimization and central composite design, the main factors in the FIL-NOSM method were optimized. Under the optimal conditions, the relative recoveries of TCS and MTCS reached up to 98.60-106.09%, and the LODs of them were as low as 0.12-0.15µgL(-1) in plasma and urine samples. In total, this [C4MIM][NPA]-based FIL-NOSM method provided high extraction efficiency, and required less pretreatment time and unutilized any organic solvent. To the best of our knowledge, this is the first application of [C4mim][NPA]-based microextraction method for the simultaneous quantification of trace TCS and MTCS in human fluids. Copyright © 2016 Elsevier B.V. All rights reserved.

[BMIM][PF(6)] promotes the synthesis of halohydrin esters from diols using potassium halides.

PubMed

Oromí-Farrús, Mireia; Eras, Jordi; Villorbina, Gemma; Torres, Mercè; Llopis-Mestre, Veronica; Welton, Tom; Canela, Ramon

2008-10-01

Haloesterification of diverse diols with various carboxylic acids was achieved using potassium halides (KX) as the only halide source in ionic liquids. The best yield was obtained in [BMIM][PF(6)] when 1,2-octanediol, palmitic acid and KBr were used. This yield was 85% and the regioisomer with the bromine in primary position was present in a 75:25 ratio. The regioisomeric ratio could be improved using either KCl or some phenylcarboxylic acids. [BMIM][PF(6)] acts as both reaction media and catalyst of the reaction. To the best of our knowledge, this type of combined reaction using an ionic liquid is unprecedented. The other solvents tested did not lead either to the same yield or to the same regioisomeric ratio.

Three cocrystals and a cocrystal salt of pyrimidin-2-amine and glutaric acid.

PubMed

Odiase, Isaac; Nicholson, Catherine E; Ahmad, Ruksanna; Cooper, Jerry; Yufit, Dmitry S; Cooper, Sharon J

2015-04-01

Four new cocrystals of pyrimidin-2-amine and propane-1,3-dicarboxylic (glutaric) acid were crystallized from three different solvents (acetonitrile, methanol and a 50:50 wt% mixture of methanol and chloroform) and their crystal structures determined. Two of the cocrystals, namely pyrimidin-2-amine-glutaric acid (1/1), C4H5N3·C6H8O4, (I) and (II), are polymorphs. The glutaric acid molecule in (I) has a linear conformation, whereas it is twisted in (II). The pyrimidin-2-amine-glutaric acid (2/1) cocrystal, 2C4H5N3·C6H8O4, (III), contains glutaric acid in its linear form. Cocrystal-salt bis(2-aminopyrimidinium) glutarate-glutaric acid (1/2), 2C4H6N3(+)·C6H6O4(2-)·2C6H8O4, (IV), was crystallized from the same solvent as cocrystal (II), supporting the idea of a cocrystal-salt continuum when both the neutral and ionic forms are present in appreciable concentrations in solution. The diversity of the packing motifs in (I)-(IV) is mainly caused by the conformational flexibility of glutaric acid, while the hydrogen-bond patterns show certain similarities in all four structures.

The history and character of acid precipitation in eastern North America

Treesearch

Charles V. Cogbill

1976-01-01

The history and present distribution of precipitation acidity in eastern North America is reviewed. Precipitation chemistry from the 1920's indicates heavy ionic deposition, but low acidity (calculated) in Tennessee (pH 7.4) and New York (pH 6.15). However, high acidity was apparently widespread over northeast North America by 1955-56 and measured pH's below...

Conductivity of gel polymer electrolytes doped with solutions of phosphonic acid or protic ionic liquids

NASA Astrophysics Data System (ADS)

Shmukler, Liudmila E.; Fadeeva, Yuliya A.; Glushenkova, Ekaterina V.; Nguyen, Van Thuc; Safonova, Liubov P.

2018-04-01

The proton-conducting gel electrolytes (PCGEs) based on PMMA, PVdF or PVdF-HFP doped with solutions of phosphonic acid or ammonium based protic ionic liquids (PILs) in DMF have been synthesized. Rather high values of the conductivity (10-4-10-3 S cm-1) have been reached at low dopant concentrations (up to 1 mol l-1). The influence of the nature of both polymeric matrix and dopant as well as dopant concentration on the conductivity values was discussed. It was established that the dependence of conductivity on the nature of dopant, but not the polymeric matrix, was more pronounced.

Effect of Brönsted acidic ionic liquid 1-(1-propylsulfonic)-3-methylimidazolium chloride on growth and co-fermentation of glucose, xylose and arabinose by Zymomonas mobilis AX101.

PubMed

Gyamerah, M; Ampaw-Asiedu, M; Mackey, J; Menezes, B; Woldesenbet, S

2018-06-01

The potential of large-scale lignocellulosic biomass hydrolysis to fermentable sugars using ionic liquids has increased interest in this green chemistry route to fermentation for fuel-ethanol production. The ionic liquid 1-(1-propylsulfonic)-3-methylimidazolium chloride compared to other reported ionic liquids has the advantage of hydrolysing lignocellulosic biomass to reducing sugars at catalytic concentrations (≤0·032 mol l -1 ) in a single step. However, effects of this ionic liquid on co-fermentation of glucose, xylose and arabinose to ethanol by recombinant Zymomonas mobilisAX101 has not been studied. Authentic glucose, xylose and arabinose were used to formulate fermentation media at varying catalytic 1-(1-propylsulfonic)-3-methylimidazolium chloride concentrations for batch co-fermentation of the sugars using Z. mobilisAX101. The results showed that at 0·008, 0·016 and 0·032 mol l -1 ionic liquid in the culture medium, cell growth decreased by 10, 27 and 67% respectively compared to the control. Ethanol yields were 62·6, 61·8, 50·5 and 23·1% for the control, 0·008, 0·016 and 0·032 mol l -1 ionic liquid respectively. The results indicate that lignocellulosic biomass hydrolysed using 0·008 mol l -1 of 1-(1-propylsulfonic)-3-methylimidazolium chloride would eliminate an additional separation step and provide a ready to use fermentation substrate. This is the first reported study of the effect of the Brönsted acidic ionic liquid 1-(1-propylsulfonic)-3-methylimidazolium chloride on growth and co-fermentation of glucose, xylose and arabinose by Zymomonas mobilisAX101 in batch culture. Growth on and co-fermentation of the sugars by Z. mobilisAX 101 with no significant inhibition by the ionic liquid at the same catalytic amounts of 0·008 mol l -1 used to hydrolyse lignocellulosic biomass to reducing sugars overcome two major hurdles that adversely affect the process economics of large-scale industrial cellulosic fuel ethanol production; the energy-intensive hydrolysis and ionic liquid separation steps. © 2018 The Society for Applied Microbiology.

Thermal boundary conductance of hydrophilic and hydrophobic ionic liquids

NASA Astrophysics Data System (ADS)

Oyake, Takafumi; Sakata, Masanori; Yada, Susumu; Shiomi, Junichiro

2015-03-01

A solid/liquid interface plays a critical role for understanding mechanisms of biological and physical science. Moreover, carrier density of the surface is dramatically enhanced by electric double layer with ionic liquid, salt in the liquid state. Here, we have measured the thermal boundary conductance (TBC) across an interface of gold thin film and ionic liquid by using time-domain thermoreflectance technique. Following the prior researches, we have identified the TBC of two interfaces. One is gold and hydrophilic ionic liquid, N,N-Diethyl-N-methyl-N-(2-methoxyethyl) ammonium tetrafluoroborate (DEME-BF4), which is a hydrophilic ionic liquid, and the other is N,N-Diethyl-N-methyl-N-(2-methoxyethyl) ammonium bis (trifluoromethanesulfonyl) imide (DEME-TFSI), which is a hydrophobic ionic liquid. We found that the TBC between gold and DEME-TFIS (19 MWm-2K-1) is surprisingly lower than the interface between gold and DEME-BF4 (45 MWm-2K-1). With these data, the importance of the wetting angle and ion concentration for the thermal transport at the solid/ionic liquid interface is discussed. Part of this work is financially supported by Japan Society for the Promotion of Science (JSPS) and Japan Science and Technology Agency. The author is financially supported by JSPS Fellowship.

Adduct formation of ionic and nanoparticular silver with amino acids and glutathione

NASA Astrophysics Data System (ADS)

Blaske, Franziska; Stork, Lisa; Sperling, Michael; Karst, Uwe

2013-09-01

To investigate the interaction of ionic and nanoparticular silver with amino acids and small peptides, an electrospray ionization time-of-flight mass spectrometry method was developed. Monomeric and oligomeric silver adducts were formed with amino acids including cysteine (Cys), methionine, histidine, lysine, or the tripeptide glutathione (GSH). The obtained spectra for ionic silver show clusters in different ratios between Ag+ and the reaction partners (X) including [Ag n X m - ( n + 1)H]- ( n = 1-4, m = 1-3). Regarding Cys, adduct clusters up to n = 5 and m = 4 were observed as well. Considering silver-GSH interactions, even doubly charged oligomers occur generating [Ag( a + 1)GSH a - ( a + 3)H]2- ( a = 5-7) and [Ag b GSH b - ( b + 2)H]2- ( b = 4-8) ions. 1H NMR data of free GSH compared to that after treatment with Ag+ confirm sulfur-metal interactions due to changing chemical shifts for the protons located adjacent to the thiol group. Density functional theory calculations for silver-GSH clusters may explain the formation of experimentally recorded large clusters due to cooperative effects between silver and carboxylic acid side chains. Both sets of experiments indicate the presence of these adducts in the liquid phase. For silver nanoparticles, the respective data confirm the release of silver ions and the subsequent adduct formation.

Sulfur tolerant hydrophobic ionic liquid solvent

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

Luebke, David; Nulwala, Hunaid; Kail, Brian

Exemplary embodiments relate to methods for removal of CO.sub.2 and other acid gases from gaseous fuels prior to combustion. Exemplary methods may be used for CO.sub.2 capture, H.sub.2 purification and natural gas sweetening. Exemplary methods use at least one ionic liquid that has excellent CO.sub.2 solubility, selectivity over hydrogen, low viscosity, and resistance to H.sub.2S.

Ionic Liquid Catalyzed Electrolyte for Electrochemical Polyaniline Supercapacitors

NASA Astrophysics Data System (ADS)

Inamdar, A. I.; Im, Hyunsik; Jung, Woong; Kim, Hyungsang; Kim, Byungchul; Yu, Kook-Hyun; Kim, Jin-Sang; Hwang, Sung-Min

2013-05-01

The effect of different wt.% of ionic liquid "1,6-bis (trimethylammonium-1-yl) hexane tetrafluoroborate" in 0.5 M LiClO4+PC electrolyte on the supercapacitor properties of polyaniline (PANI) thin film are investigated. The PANI film is synthesized using electropolymerization of aniline in the presence of sulfuric acid. The electrochemical properties of the PANI thin film are studied by cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy (EIS) measurements. The optimum amount of the ionic liquid is found to be 2 wt.% which provides better ionic conductivity of the electrolyte. The highest specific capacitance of 259 F/g is obtained using the 2 wt.% electrolyte. This capacitance remains at up to 208 F/g (80% capacity retention) after 1000 charge-discharge cycles at a current density of 0.5 mA/g. The PANI film in the 2 wt.% ionic liquid catalyzed 0.5 M LiClO4+PC electrolyte shows small electrochemical resistance, better rate performance and higher cyclability. The increased ionic conductivity of the 2 wt.% ionic liquid catalyzed electrolyte causes a reduction in resistance at the electrode/electrolyte interface, which can be useful in electrochemically-preferred power devices for better applicability.

AIE-doped poly(ionic liquid) photonic spheres: a single sphere-based customizable sensing platform for the discrimination of multi-analytes† †Electronic supplementary information (ESI) available: Synthesis and characterization of the AIE luminogen, experimental details, response profiles and results of the multivariate analysis. See DOI: 10.1039/c7sc02409f Click here for additional data file.

PubMed Central

Zhang, Wanlin; Gao, Ning; Cui, Jiecheng; Wang, Chen; Wang, Shiqiang; Zhang, Guanxin; Dong, Xiaobiao

2017-01-01

By simultaneously exploiting the unique properties of ionic liquids and aggregation-induced emission (AIE) luminogens, as well as photonic structures, a novel customizable sensing system for multi-analytes was developed based on a single AIE-doped poly(ionic liquid) photonic sphere. It was found that due to the extraordinary multiple intermolecular interactions involved in the ionic liquid units, one single sphere could differentially interact with broader classes of analytes, thus generating response patterns with remarkable diversity. Moreover, the optical properties of both the AIE luminogen and photonic structure integrated in the poly(ionic liquid) sphere provide multidimensional signal channels for transducing the involved recognition process in a complementary manner and the acquisition of abundant and sufficient sensing information could be easily achieved on only one sphere sensor element. More importantly, the sensing performance of our poly(ionic liquid) photonic sphere is designable and customizable through a simple ion-exchange reaction and target-oriented multi-analyte sensing can be conveniently realized using a selective receptor species, such as counterions, showing great flexibility and extendibility. The power of our single sphere-based customizable sensing system was exemplified by the successful on-demand detection and discrimination of four multi-analyte challenge systems: all 20 natural amino acids, nine important phosphate derivatives, ten metal ions and three pairs of enantiomers. To further demonstrate the potential of our spheres for real-life application, 20 amino acids in human urine and their 26 unprecedented complex mixtures were also discriminated between by the single sphere-based array. PMID:28989662

Enzymatic hybridization of α-lipoic acid with bioactive compounds in ionic solvents.

PubMed

Papadopoulou, Athena A; Katsoura, Maria H; Chatzikonstantinou, Alexandra; Kyriakou, Eleni; Polydera, Angeliki C; Tzakos, Andreas G; Stamatis, Haralambos

2013-05-01

The lipase-catalyzed molecular hybridization of α-lipoic acid (LA) with bioactive compounds pyridoxine, tyrosol and tyramine was performed in ionic solvents and deep eutectic solvents. The biocatalytic reactions were catalyzed by Candida antarctica lipase B immobilized onto various functionalized multi-walled carbon nanotubes (f-CNTs-CaLB), as well as by commercial Novozym 435. The use of f-CNTs-CaLB leads, in most cases, to higher conversion yields as compared to Novozym 435. The nature and ion composition of ionic solvents affect the performance of the biocatalytic process. The highest conversion yield was observed in (mtoa)NTf2. The high enzyme stability and the relatively low solubility of substrates in specific media account for the improved biocatalytic synthesis of molecular hybrids of LA. Principal component analysis was used to screen for potential lipoxygenase inhibitors. In vitro studies showed that the synthesized compounds exhibit up to 10-fold increased inhibitory activity on lipoxygenase mediated lipid peroxidation as compared to parent molecules. Copyright © 2013 Elsevier Ltd. All rights reserved.

Ionic liquid as a mobile phase additive in high-performance liquid chromatography for the simultaneous determination of eleven fluorescent whitening agents in paper materials.

PubMed

Wang, Qing; Chen, Xianbo; Qiu, Bin; Zhou, Liang; Zhang, Hui; Xie, Juan; Luo, Yan; Wang, Bin

2016-04-01

In the present study, 11 4,4'-diaminostilbene-2,2'-disulfonic acid based fluorescent whitening agents with different numbers of sulfonic acid groups were separated by using an ionic liquid as a mobile phase additive in high-performance liquid chromatography with fluorescence detection. The effects of ionic liquid concentration, pH of mobile phase B, and composition of mobile phase A on the separation of fluorescent whitening agents were systematically investigated. The ionic liquid tetrabutylammonium tetrafluoroborate is superior to tetrabutylammomnium bromide for the separation of the fluorescent whitening agents. The optimal separation conditions were an ionic liquid concentration at 8 mM and the pH of mobile phase B at 8.5 with methanol as mobile phase A. The established method exhibited low limits of detection (0.04-0.07 ng/mL) and wide linearity ranges (0.30-20 ng/mL) with high linear correlation coefficients from 0.9994 to 0.9998. The optimized procedure was applied to analyze target analytes in paper samples with satisfactory results. Eleven target analytes were quantified, and the recoveries of spiked paper samples were in the range of 85-105% with the relative standard deviations from 2.1 to 5.1%. The obtained results indicated that the method was efficient for detection of 11 fluorescent whitening agents. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Direct Production of Furfural in One-pot Fashion from Raw Biomass Using Brønsted Acidic Ionic Liquids.

PubMed

Matsagar, Babasaheb M; Hossain, Shahriar A; Islam, Tofazzal; Alamri, Hatem R; Alothman, Zeid A; Yamauchi, Yusuke; Dhepe, Paresh L; Wu, Kevin C-W

2017-10-18

The conversion of raw biomass into C5-sugars and furfural was demonstrated with the one-pot method using Brønsted acidic ionic liquids (BAILs) without any mineral acids or metal halides. Various BAILs were synthesized and characterized using NMR, FT-IR, TGA, and CHNS microanalysis and were used as the catalyst for raw biomass conversion. The remarkably high yield (i.e. 88%) of C5 sugars from bagasse can be obtained using 1-methyl-3(3-sulfopropyl)-imidazolium hydrogen sulfate ([C 3 SO 3 HMIM][HSO 4 ]) BAIL catalyst in a water medium. Similarly, the [C 3 SO 3 HMIM][HSO 4 ] BAIL also converts the bagasse into furfural with very high yield (73%) in one-pot method using a water/toluene biphasic solvent system.

Mapping the pharmaceutical design space by amorphous ionic liquid strategies.

PubMed

Wiest, Johannes; Saedtler, Marco; Balk, Anja; Merget, Benjamin; Widmer, Toni; Bruhn, Heike; Raccuglia, Marc; Walid, Elbast; Picard, Franck; Stopper, Helga; Dekant, Wolfgang; Lühmann, Tessa; Sotriffer, Christoph; Galli, Bruno; Holzgrabe, Ulrike; Meinel, Lorenz

2017-12-28

Poor water solubility of drugs fuels complex formulations and jeopardizes patient access to medication. Simplifying these complexities we systematically synthesized a library of 36 sterically demanding counterions and mapped the pharmaceutical design space for amorphous ionic liquid strategies for Selurampanel, a poorly water soluble drug used against migraine. Patients would benefit from a rapid uptake after oral administration to alleviate migraine symptoms. Therefore, we probed the ionic liquids for the flux, supersaturation period and hygroscopicity leading to algorithms linking molecular counterion descriptors to predicted pharmaceutical outcome. By that, 30- or 800-fold improvements of the supersaturation period and fluxes were achieved as were immediate to sustained release profiles through structural counterions' optimization compared to the crystalline free acid of Selurampanel. Guided by ionic liquid structure, in vivo profiles ranged from rapid bioavailability and high maximal plasma concentrations to sustained patterns. In conclusion, the study outlined and predicted the accessible pharmaceutical design space of amorphous ionic liquid based and excipient-free formulations pointing to the enormous pharmaceutical potential of ionic liquid designs. Copyright © 2017 Elsevier B.V. All rights reserved.

Glucose transformation to 5-hydroxymethylfurfural in acidic ionic liquid: A quantum mechanical study.

PubMed

Arifin; Puripat, Maneeporn; Yokogawa, Daisuke; Parasuk, Vudhichai; Irle, Stephan

2016-01-30

Isomerization and transformation of glucose and fructose to 5-hydroxymethylfurfural (HMF) in both ionic liquids (ILs) and water has been studied by the reference interaction site model self-consistent field spatial electron density distribution (RISM-SCF-SEDD) method coupled with ab initio electronic structure theory, namely coupled cluster single, double, and perturbative triple excitation (CCSD(T)). Glucose isomerization to fructose has been investigated via cyclic and open chain mechanisms. In water, the calculations support the cyclic mechanism of glucose isomerization; with the predicted activation free energy is 23.8 kcal mol(-1) at experimental condition. Conversely, open ring mechanism is more favorable in ILs with the energy barrier is 32.4 kcal mol(-1) . Moreover, the transformation of fructose into HMF via cyclic mechanism is reasonable; the calculated activation barriers are 16.0 and 21.5 kcal mol(-1) in aqueous and ILs solutions, respectively. The solvent effects of ILs could be explained by the decomposition of free energies and radial distribution functions of solute-solvent that are produced by RISM-SCF-SEDD. © 2015 Wiley Periodicals, Inc.

Selective Attachment of Nucleic Acid Molecules to Patterned Self-Assembled Surfaces.

DTIC Science & Technology

1994-12-01

of different sequence is accomplished by placement of 8 liquid portions of nucleic acids at the desired position on the 9 filter. This method is...acids are selectively 24 bound from regions to which nucleic acids are excluded, other than 25 by placement of liquid aliquots (generally >1 Al) of...is typically non-covalent (i.e., ionic 16 bonding, or, less often, hydrogen bonding). Advantageously, non- 17 covalent bonding of nucleic acid

Perchlorate and Halogen-Free High Energy Dense Oxidizers (HEDO)

DTIC Science & Technology

2011-06-01

nitric acid indicate that the covalent oxalic acid dinitrate ester should be more stable than the ionic dinitronium oxalate . The following three...synthetic strategies were developed to generate compound 11 (Scheme 17). Strategy I is the nitration of anhydrous oxalic acid with nitric acid (100...temperatures (25 to –30 °C) and in all dry solvents used. Scheme 17: Synthetic strategies for the production of oxalic acid dinitrate ester (11

The effect of humic acid on uranyl sorption onto bentonite at trace uranium levels.

PubMed

Ivanov, Peter; Griffiths, Tamara; Bryan, Nick D; Bozhikov, Gospodin; Dmitriev, Serguei

2012-11-01

The effect of humic acid (HA) on U(VI) sorption on bentonite was studied in batch experiments at room temperature and ambient atmosphere at a (237)U(VI) concentration of 8.4 × 10(-11) M and HA concentration of 100 mg L(-1). The distribution of U(VI) between the liquid and solid phases was studied as a function of pH and ionic strength both in the absence and presence of HA. It was shown that the uranyl sorption on bentonite is strongly dependent on pH and the presence of humics, and the effect of the addition order was negligible. In the absence of HA an enhancement in the uptake with increasing pH was observed and a sharp sorption edge was found to take place between pH 3.2 and 4.2. The presence of HA slightly increases uranium(VI) sorption at low pH and curtails it at moderate pH, compared to the absence of HA. In the basic pH range for both the presence and absence of HA the sorption of uranium is significantly reduced, which could be attributed to the formation of soluble uranyl carbonate complexes. The influence of ionic strength on U(VI) and HA uptake by bentonite were investigated in the range of 0.01-1.0 M, and while there was an enhancement in the sorption of humic acid with increasing ionic strength, no significant effect of the ionic strength on the U(VI) sorption was observed in both the absence and presence of HA.

Metallurgical characterization, galvanic corrosion, and ionic release of orthodontic brackets coupled with Ni-Ti archwires.

PubMed

Darabara, Myrsini S; Bourithis, Lefteris I; Zinelis, Spiros; Papadimitriou, George D

2007-04-01

In orthodontics, a combination of metallic alloys is placed into the oral cavity during medical treatment and thus the corrosion resistance and ionic release of these appliances is of vital importance. The aim of this study is to investigate the elemental composition, microstructure, hardness, corrosion properties, and ionic release of commercially available orthodontic brackets and Copper Ni-Ti archwires. Following the assessment of the elemental composition of the orthodontic wire (Copper Ni-Ti) and the six different brackets (Micro Loc, Equilibrium, OptiMESH(XRT), Gemini, Orthos2, and Rematitan), cyclic polarization curves were obtained for each material to estimate the susceptibility of each alloy to pitting corrosion in 1M lactic acid. Galvanic corrosion between the orthodontic wire and each bracket took place in 1M lactic acid for 28 days at 37 degrees C and then the ionic concentration of Nickel and Chromium was studied. The orthodontic wire is made up from a Ni-Ti alloy with copper additions, while the orthodontic brackets are manufactured by different stainless steel grades or titanium alloys. All tested wires and brackets with the exception of Gemini are not susceptible to pitting corrosion. In galvanic corrosion, following exposure for 28 days, the lowest potential difference (approximately 250 mV) appears for the orthodontic wire Copper Ni-Ti and the bracket made up from pure titanium (Rematitan) or from the stainless steel AISI 316 grade (Micro Loc). Following completion of the galvanic corrosion experiments, measurable quantities of chromium and nickel ions were found in the residual lactic acid solution. (c) 2006 Wiley Periodicals, Inc.

Chromatographic Separation, and Characteristics of Nucleic Acids from HeLa Cells

PubMed Central

Philipson, Lennart

1961-01-01

The application of the phenol-duponol method to extraction of nucleic acids from HeLa cells is described. Chromatography of the phenol extract on an esterified bovine serum albumin column with a salt gradient of sodium chloride gives separation of soluble RNA, DNA, and two different high molecular RNA fractions. Ultracentrifugation of the DNA eluted from the column gives a sedimentation coefficient (s 20 o,w) of 38, which agrees with ultracentrifugation data on the phenol extract. The eluted RNA appears polydisperse at low ionic strength, but at high ionic strength and after alcohol precipitation two fractions with the sedimentation coefficients of 16 and 25 to 29, respectively, were obtained. PMID:13735276

Experimental determination of solubilities of di-calcium ethylenediaminetetraacetic acid hydrate [Ca2C10H12N2O8·7H2O(s)] in NaCl and MgCl2 solutions to high ionic strengths and its Pitzer model: Applications to geological disposal of nuclear waste and other low temperature environments

DOE PAGES

Xiong, Yongliang; Kirkes, Leslie; Westfall, Terry

2017-04-01

In this study, solubility measurements on di-calcium ethylenediaminetetraacetic acid [Ca 2C 10H 12N 2O 8(s), abbreviated as Ca 2EDTA(s)] as a function of ionic strength are conducted in NaCl solutions up to I = 5.0 mol•kg –1 and in MgCl 2 solutions up to I = 7.5 mol•kg –1, at room temperature (22.5 ± 0.5oC).

Separation of the fatty acids in menhaden oil as methyl esters with a highly polar ionic liquid gas chromatographic column and identification by time of flight mass spectrometry.

PubMed

Fardin-Kia, Ali Reza; Delmonte, Pierluigi; Kramer, John K G; Jahreis, Gerhard; Kuhnt, Katrin; Santercole, Viviana; Rader, Jeanne I

2013-12-01

The fatty acids contained in marine oils or products are traditionally analyzed by gas chromatography using capillary columns coated with polyethylene glycol phases. Recent reports indicate that 100 % cyanopropyl siloxane phases should also be used when the analyzed samples contain trans fatty acids. We investigated the separation of the fatty acid methyl esters prepared from menhaden oil using the more polar SLB-IL111 (200 m × 0.25 mm) ionic liquid capillary column and the chromatographic conditions previously optimized for the separation of the complex mixture of fatty acid methyl esters prepared from milk fat. Identifications of fatty acids were achieved by applying Ag(+)-HPLC fractionation and GC-TOF/MS analysis in CI(+) mode with isobutane as the ionization reagent. Calculation of equivalent chain lengths confirmed the assignment of double bond positions. This methodology allowed the identification of 125 fatty acids in menhaden oil, including isoprenoid and furanoid fatty acids, and the novel 7-methyl-6-hexadecenoic and 7-methyl-6-octadecenoic fatty acids. The chromatographic conditions applied in this study showed the potential of separating in a single 90-min analysis, among others, the short chain and trans fatty acids contained in dairy products, and the polyunsaturated fatty acids contained in marine products.

Functionalization of carbon nanotubes with water-insoluble porphyrin in ionic liquid: direct electrochemistry and highly sensitive amperometric biosensing for trichloroacetic acid.

PubMed

Tu, Wenwen; Lei, Jianping; Ju, Huangxian

2009-01-01

A functional composite of single-walled carbon nanotubes (SWNTs) with hematin, a water-insoluble porphyrin, was first prepared in 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF(6)]) ionic liquid. The novel composite in ionic liquid was characterized by scanning electron microscopy, ultraviolet absorption spectroscopy, and electrochemical impedance spectroscopy, and showed a pair of direct redox peaks of the Fe(III)/Fe(II) couple. The composite-[BMIM][PF(6)]-modified glassy carbon electrode showed excellent electrocatalytic activity toward the reduction of trichloroacetic acid (TCA) in neutral media due to the synergic effect among SWNTs, [BMIM][PF(6)], and porphyrin, which led to a highly sensitive and stable amperometric biosensor for TCA with a linear range from 9.0x10(-7) to 1.4x10(-4) M. The detection limit was 3.8x10(-7) M at a signal-to-noise ratio of 3. The TCA biosensor had good analytical performance, such as rapid response, good reproducibility, and acceptable accuracy, and could be successfully used for the detection of residual TCA in polluted water. The functional composite in ionic liquid provides a facile way to not only obtain the direct electrochemistry of water-insoluble porphyrin, but also construct novel biosensors for monitoring analytes in real environmental samples.

Innovative Poly(Ionic Liquid)s by the Polymerization of Deep Eutectic Monomers.

PubMed

Isik, Mehmet; Ruiperez, Fernando; Sardon, Haritz; Gonzalez, Alba; Zulfiqar, Sonia; Mecerreyes, David

2016-07-01

The incorporation of ionic liquid (IL) chemistry into functional polymers has extended the properties and applications of polyelectrolytes. However, ILs are expensive due to the presence of fluorinated anions or complicated synthetic steps which limit their technological viability. Here, we show a new family of poly(ionic liquid)s (PILs) which are based in cheap and renewable chemicals and involves facile synthetic approaches. Thus, deep eutectic monomers (DEMs) are prepared for the first time by using quaternary ammonium compounds and various hydrogen bond donors such as citric acid, terephthalic acid or an amidoxime. The deep eutectic formation is made through a simple mixing of the ingredients. Differential scanning calorimetry, nuclear magnetic resonance (NMR) and computational studies reveal the formation of the DEMs due to the ionic interactions. The resulting DEMs are liquid which facilitates their polymerization using mild photopolymerization or polycondensation strategies. Spectroscopic characterizations reveal the successful formation of the polymers. By this way, a new family of PILs can be synthesized which can be used for different applications. As an example, the polymers show promising performance as solid CO2 sorbents. Altogether the deep eutectic monomer route can lead to non-toxic, cheap and easy-to-prepare alternatives to current PILs for different applications. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DNA surface hybridization regimes

PubMed Central

Gong, Ping; Levicky, Rastislav

2008-01-01

Surface hybridization reactions, in which sequence-specific recognition occurs between immobilized and solution nucleic acids, are routinely carried out to quantify and interpret genomic information. Although hybridization is fairly well understood in bulk solution, the greater complexity of an interfacial environment presents new challenges to a fundamental understanding, and hence application, of these assays. At a surface, molecular interactions are amplified by the two-dimensional nature of the immobilized layer, which focuses the nucleic acid charge and concentration to levels not encountered in solution, and which impacts the hybridization behavior in unique ways. This study finds that, at low ionic strengths, an electrostatic balance between the concentration of immobilized oligonucleotide charge and solution ionic strength governs the onset of hybridization. As ionic strength increases, the importance of electrostatics diminishes and the hybridization behavior becomes more complex. Suppression of hybridization affinity constants relative to solution values, and their weakened dependence on the concentration of DNA counterions, indicate that the immobilized strands form complexes that compete with hybridization to analyte strands. Moreover, an unusual regime is observed in which the surface coverage of immobilized oligonucleotides does not significantly influence the hybridization behavior, despite physical closeness and hence compulsory interactions between sites. These results are interpreted and summarized in a diagram of hybridization regimes that maps specific behaviors to experimental ranges of ionic strength and probe coverage. PMID:18381819

Effects of alkyl chain length and solvents on thermodynamic dissociation constants of the ionic liquids with one carboxyl group in the alkyl chain of imidazolium cations.

PubMed

Chen, Yuehua; Wang, Huiyong; Wang, Jianji

2014-05-01

Thermodynamic dissociation constants of the Brønsted acidic ionic liquids (ILs) are important for their catalytic and separation applications. In this work, a series of imidazolium bromides with one carboxylic acid substitute group in their alkyl chain ([{(CH2)nCOOH}mim]Br, n = 1,3,5,7) have been synthesized, and their dissociation constants (pKa) at different ionic strengths have been determined in aqueous and aqueous organic solvents at 0.1 mole fraction (x) of ethanol, glycol, iso-propanol, and dimethyl sulfoxide by potentiometric titrations at 298.2 K. The standard thermodynamic dissociation constants (pKa(T)) of the ILs in these solvents were calculated from the extended Debye-Hückel equation. It was found that the pKa values increased with the increase of ionic strength of the media and of the addition of organic solvent in water. The pKa(T) values also increased with the increase of the alkyl chain length of cations of the ILs. In addition, the effect of solvent nature on pKa(T) values is interpreted from solvation of the dissociation components and their Gibbs energy of transfer from water to aqueous organic solutions.

Ionic liquids as transesterification catalysts: applications for the synthesis of linear and cyclic organic carbonates

PubMed Central

Perosa, Alvise; Guidi, Sandro; Cattelan, Lisa

2016-01-01

Summary The use of ionic liquids (ILs) as organocatalysts is reviewed for transesterification reactions, specifically for the conversion of nontoxic compounds such as dialkyl carbonates to both linear mono-transesterification products or alkylene carbonates. An introductory survey compares pros and cons of classic catalysts based on both acidic and basic systems, to ionic liquids. Then, innovative green syntheses of task-specific ILs and their representative applications are introduced to detail the efficiency and highly selective outcome of ILs-catalyzed transesterification reactions. A mechanistic hypothesis is discussed by the concept of cooperative catalysis based on the dual (electrophilic/nucleophilic) activation of reactants. PMID:27829898

Ionic liquids as stationary phases for fatty acid analysis by gas chromatography.

PubMed

Fanali, C; Micalizzi, G; Dugo, P; Mondello, L

2017-12-04

The present paper provides an overview of the application of ionic liquid (IL) columns for GC analysis of fatty acid methyl esters (FAMEs). Although their separation can be carried out utilizing GC columns containing polar stationary phases, some ILs have been employed as stationary phases, either commercial or laboratory made, in GC analysis. Monodimensional and bidimensional GC methods have been optimized in order to achieve the best separation especially considering the geometric and positional isomers of unsaturated fatty acids. Several methods for the analysis of trans-fatty acids have also been reported. The use of GC-GC, using either the same IL columns or different columns in the first and second dimensions, allowed the separation of a large number of FAMEs. The application of the IL columns for GC analysis of FAMEs in different types of real samples is described, e.g., oil of different nature (fish, flaxseed, and olive), margarine and butter, biodiesel, milk, bacteria etc.

A study on the effect of the concentration of N,N-methylenebisacrylamide and acrylic acid toward the properties of Dioscorea hispida-starch-based hydrogel

NASA Astrophysics Data System (ADS)

Ashri, Airul; Lazim, Azwan

2014-09-01

The research investigated the effects of acrylic acid (monomer) and N,N,-methylenebisacrylamide, MBA (crosslinker) toward the percentage of gel content, swelling ratio and ionic strength of a starch-based hydrogel. Starch grafted on poly (sodium acrylate), St-g-PAANa hydrogel was prepared by incorporating starch extracted from Dioscorea hispida in NaOH/aqueous solution using different composition of acrylic acid (AA) and N,N-methylenebisacrylamide (MBA) in the presence of potassium persulfate (KPS) as chemical initiator. The highest gel content was observed at 1:30 ratio of starch to AA and 0.10 M of MBA. Results showed the highest swelling ratio was observed at 1:15 ratio of starch to acrylic acid and 0.02 M of MBA solution. The same results also gave the highest swelling ratio for the ionic strength study. The FTIR analysis was also conducted in order to confirm the grafting of AA onto starch backbone.

Effect of the ionic strength of a mobile phase on the chromatographic retention and thermodynamic characteristics of the adsorption of enantiomers of α-phenylcarboxylic acids on a chiral adsorbent with grafted antibiotic eremomycin

NASA Astrophysics Data System (ADS)

Reshetova, E. N.

2017-01-01

The effect the ionic strength of an aqueous ethanol mobile phase containing buffer salt has the on retention and thermodynamics of adsorption of optical isomers of some α-phenylcarboxylic acids on chiral adsorbent Nautilus-E with grafted antibiotic eremomycin is investigated. It is shown that ion exchange processes participate in the adsorption of enantiomers of α-phenylcarboxylic acids. It is established that electrostatic interactions contribute to the retention of enantiomers of α-phenylcarboxylic acids and affect selectivity only slightly. The dependences of retention characteristics, selectivity, and thermodynamic parameters on the concentration of the buffer salt in the eluent are determined. A statistical analysis of enthalpy-entropy compensation is performed, and the compensation effect is shown to be true. It is found that the points corresponding to the investigated adsorbates are distributed over the compensation dependence according to the spatial structural characteristics of molecules.

Biodiesel from Citrullus colocynthis Oil: Sulfonic-Ionic Liquid-Catalyzed Esterification of a Two-Step Process

PubMed Central

Ali Elsheikh, Yasir; Hassan Akhtar, Faheem

2014-01-01

Biodiesel was prepared from Citrullus colocynthis oil (CCO) via a two-step process. The first esterification step was explored in two ionic liquids (ILs) with 1,3-disulfonic acid imidazolium hydrogen sulfate (DSIMHSO4) and 3-methyl-1-sulfonic acid imidazolium hydrogen sulfate (MSIMHSO4). Both ILs appeared to be good candidates to replace hazardous acidic catalyst due to their exceptional properties. However, the two sulfonic chains existing in DSIMHSO4 were found to increase the acidity to the IL than the single sulfonic chain in MSIMHSO4. Based on the results, 3.6 wt% of DSIMHSO4, methanol/CCO molar ratio of 12 : 1, and 150°C offered a final FFA conversion of 95.4% within 105 min. A 98.2% was produced via second KOH-catalyzed step in 1.0%, 6 : 1 molar ratio, 600 rpm, and 60°C for 50 min. This new two-step catalyzed process could solve the corrosion and environmental problems associated with the current acidic catalysts. PMID:24987736

Gas-Phase Anionic σ-Adduct (Trans)formations in Heteroaromatic Systems1

NASA Astrophysics Data System (ADS)

Zimnicka, Magdalena; Danikiewicz, Witold

2015-07-01

Anions of nitroderivatives of thiophene and furan were subjected to the reactions with selected C-H acids in the gas phase. Various structures and reaction pathways were proposed for the observed ionic products. In general, the reactions of heteroaromatic anions with C-H acids may be divided into three groups, depending on the proton affinity difference between C-H acid's conjugate base and heteroaromatic anion (ΔPA). The proton transfer from C-H acid to heteroaromatic anion is a dominant process in the reactions for which ΔPA < 0 kcal mol-1, whereas the reactions with high ΔPA (ΔPA > 16 kcal mol-1) do not lead to any ionic products. The formation of σ-adducts and products of their further transformations according to the VNS, SNAr, cine, and tele substitution mechanisms have been proposed for reactions with moderate ΔPA. The other possible mechanisms as SN2 reaction, nucleophilic addition to the cyano group, ring-opening pathway, and halogenophilic reaction have also been discussed to contribute in the reactions between heteroaromatic anions and C-H acids.

Tuning the Selectivity of Single-Site Supported Metal Catalysts with Ionic Liquids

DOE PAGES

Babucci, Melike; Fang, Chia -Yu; Hoffman, Adam S.; ...

2017-09-11

1,3-Dialkylimidazolium ionic liquid coatings act as electron donors, increasing the selectivity for partial hydrogenation of 1,3-butadiene catalyzed by iridium complexes supported on high-surface-area γ-Al 2O 3. High-energy-resolution fluorescence detection X-ray absorption near-edge structure (HERFD XANES) measurements quantify the electron donation and are correlated with the catalytic activity and selectivity. Furthermore, the results demonstrate broad opportunities to tune electronic environments and catalytic properties of atomically dispersed supported metal catalysts.

Process intensification of biodiesel production by using microwave and ionic liquids as catalyst

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

Handayani, Prima Astuti; Chemical Engineering Program, Faculty of Engineering, Semarang State University; Abdullah

The energy crisis pushes the development and intensification of biodiesel production process. Biodiesel is produced by transesterification of vegetable oils or animal fats and conventionally produced by using acid/base catalyst. However, the conventional method requires longer processing time and obtains lower yield of biodiesel. The microwave has been intensively used to accelerate production process and ionic liquids has been introduced as source of catalyst. This paper discusses the overview of the development of biodiesel production through innovation using microwave irradiation and ionic liquids catalyst to increase the yield of biodiesel. The potential microwave to reduce the processing time will bemore » discussed and compared with other energy power, while the ionic liquids as a new generation of catalysts in the chemical industry will be also discussed for its use. The ionic liquids has potential to enhance the economic and environmental aspects because it has a low corrosion effect, can be recycled, and low waste form.« less

Process intensification of biodiesel production by using microwave and ionic liquids as catalyst

NASA Astrophysics Data System (ADS)

Handayani, Prima Astuti; Abdullah, dan Hadiyanto

2015-12-01

The energy crisis pushes the development and intensification of biodiesel production process. Biodiesel is produced by transesterification of vegetable oils or animal fats and conventionally produced by using acid/base catalyst. However, the conventional method requires longer processing time and obtains lower yield of biodiesel. The microwave has been intensively used to accelerate production process and ionic liquids has been introduced as source of catalyst. This paper discusses the overview of the development of biodiesel production through innovation using microwave irradiation and ionic liquids catalyst to increase the yield of biodiesel. The potential microwave to reduce the processing time will be discussed and compared with other energy power, while the ionic liquids as a new generation of catalysts in the chemical industry will be also discussed for its use. The ionic liquids has potential to enhance the economic and environmental aspects because it has a low corrosion effect, can be recycled, and low waste form.

Electrochemical Impedance Spectrometer with an Environmental Chamber for Rapid Screening of New Precise Copolymers

DTIC Science & Technology

2017-10-07

polymerization to make linear polyethylenes with carboxylic acid groups at precise intervals along the polymer . Precise acid- containing polymers provide...acid polyethylene and the a polymerized ionic liquids based on cyclopropenium. The instrument is also be used to study polymer segmental dynamics...Advances in batteries, fuel cells, and permselective membranes are materials limited. New acid- and ion-containing polymers must be designed and

Kinetics of gibbsite dissolution under low ionic strength conditions

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

Ganor, J.; Mogollon, J.L.; Lasaga, A.C.

1999-06-01

Experiments measuring synthetic gibbsite dissolution rates were carried out using both a stirred-flow-through reactor and a column reactor at 25 C, and pH range of 2.5--4.1. All experiments were conducted under far from equilibrium conditions ({Delta}G < {minus}1.1 kcal/mole). The experiments were performed with perchloric acid under relatively low (and variable) ionic strength conditions. An excellent agreement was found between the results of the well-mixed flow-through experiments and those of the (nonmixed) column experiments. This agreement shows that the gibbsite dissolution rate is independent of the stirring rate and therefore supports the conclusion of Bloom and Erich (1987) that gibbsitemore » dissolution reaction is surface controlled and not diffusion controlled. The Brunauer-Emmett-Teller (BET) surface area of the gibbsite increased during the flow-through experiments, while in the column experiments no significant change in surface area was observed. The significant differences in the BET surface area between the column experiments and the flow-through experiments, and the excellent agreement between the rates obtained by both methods, enable the authors to justify the substitution of the BET surface area for the reactive surface area. The dissolution rate of gibbsite varied as a function of the perchloric acid concentration. The authors interpret the gibbsite dissolution rate as a result of a combined effect of proton catalysis and perchlorate inhibition. Following the theoretical study of Ganor and Lasaga (1998) they propose specific reaction mechanisms for the gibbsite dissolution in the presence of perchloric acid. The mathematical predictions of two of these reaction mechanisms adequately describe the experimental data.« less

Electrostatic Steering Accelerates C3d:CR2 Association

PubMed Central

2016-01-01

Electrostatic effects are ubiquitous in protein interactions and are found to be pervasive in the complement system as well. The interaction between complement fragment C3d and complement receptor 2 (CR2) has evolved to become a link between innate and adaptive immunity. Electrostatic interactions have been suggested to be the driving factor for the association of the C3d:CR2 complex. In this study, we investigate the effects of ionic strength and mutagenesis on the association of C3d:CR2 through Brownian dynamics simulations. We demonstrate that the formation of the C3d:CR2 complex is ionic strength-dependent, suggesting the presence of long-range electrostatic steering that accelerates the complex formation. Electrostatic steering occurs through the interaction of an acidic surface patch in C3d and the positively charged CR2 and is supported by the effects of mutations within the acidic patch of C3d that slow or diminish association. Our data are in agreement with previous experimental mutagenesis and binding studies and computational studies. Although the C3d acidic patch may be locally destabilizing because of unfavorable Coulombic interactions of like charges, it contributes to the acceleration of association. Therefore, acceleration of function through electrostatic steering takes precedence to stability. The site of interaction between C3d and CR2 has been the target for delivery of CR2-bound nanoparticle, antibody, and small molecule biomarkers, as well as potential therapeutics. A detailed knowledge of the physicochemical basis of C3d:CR2 association may be necessary to accelerate biomarker and drug discovery efforts. PMID:27092816

New porous monolithic membranes based on supported ionic liquid-like phases for oil/water separation and homogenous catalyst immobilisation.

PubMed

Porcar, Raúl; Nuevo, Daniel; García-Verdugo, Eduardo; Lozano, Pedro; Sanchez-Marcano, José; Burguete, M Isabel; Luis, Santiago V

2018-03-07

Porous monolithic advanced functional materials based on supported ionic liquid-like phase (SILLP) systems were used for the preparation of oleophilic and hydrophobic cylindrical membranes and successfully tested as eco-friendly and safe systems for oil/water separation and for the continuous integration of catalytic and separation processes in an aqueous-organic biphasic reaction system.

Ionic liquid-based materials: a platform to design engineered CO2 separation membranes.

PubMed

Tomé, Liliana C; Marrucho, Isabel M

2016-05-21

During the past decade, significant advances in ionic liquid-based materials for the development of CO2 separation membranes have been accomplished. This review presents a perspective on different strategies that use ionic liquid-based materials as a unique tuneable platform to design task-specific advanced materials for CO2 separation membranes. Based on compilation and analysis of the data hitherto reported, we provide a judicious assessment of the CO2 separation efficiency of different membranes, and highlight breakthroughs and key challenges in this field. In particular, configurations such as supported ionic liquid membranes, polymer/ionic liquid composite membranes, gelled ionic liquid membranes and poly(ionic liquid)-based membranes are detailed, discussed and evaluated in terms of their efficiency, which is attributed to their chemical and structural features. Finally, an integrated perspective on technology, economy and sustainability is provided.

SN2 fluorination reactions in ionic liquids: a mechanistic study towards solvent engineering.

PubMed

Oh, Young-Ho; Jang, Hyeong Bin; Im, Suk; Song, Myoung Jong; Kim, So-Yeon; Park, Sung-Woo; Chi, Dae Yoon; Song, Choong Eui; Lee, Sungyul

2011-01-21

In the catalysis of S(N)2 fluorination reactions, the ionic liquid anion plays a key role as a Lewis base by binding to the counterion Cs(+) and thereby reducing the retarding Coulombic influence of Cs(+) on the nucleophile F(-). The reaction rates also depend critically on the structures of ionic liquid cation, for example, n-butyl imidazolium gives no S(N)2 products, whereas n-butylmethyl imidazolium works well. The origin of the observed phenomenal synergetic effects by the ionic liquid [mim-(t)OH][OMs], in which t-butanol is bonded covalently to the cation [mim], is that the t-butanol moiety binds to the leaving group of the substrate, moderating the retarding interactions between the acidic hydrogen and F(-). This work is a significant step toward designing and engineering solvents for promoting specific chemical reactions.

Intermolecular ionic cross-linked sulfonated poly(ether ether ketone) membranes containing diazafluorene for direct methanol fuel cell applications

NASA Astrophysics Data System (ADS)

Liang, Yu; Gong, Chenliang; Qi, Zhigang; Li, Hui; Wu, Zhongying; Zhang, Yakui; Zhang, Shujiang; Li, Yanfeng

2015-06-01

A series of novel ionic cross-linking sulfonated poly(ether ether ketone) (SPEEK) membranes containing the diazafluorene functional group are synthesized to reduce the swelling ratio and methanol permeability for direct methanol fuel cell (DMFC) applications. The ionic cross-linking is realized by the interaction between sulfonic acid groups and pyridyl in diazafluorene. The prepared membranes exhibit good mechanical properties, adequate thermal stability, good oxidative stability, appropriate water uptake and low swelling ratio. Moreover, the ionic cross-linked membranes exhibit lower methanol permeability in the range between 0.56 × 10-7 cm2 s-1 and 1.8 × 10-7 cm2 s-1, which is lower than Nafion 117, and they exhibit higher selectivity than Nafion 117 at 30 °C on the basis of applicable proton conductivity.

Quantifying the effect of ionic screening with protein-decorated graphene transistors

PubMed Central

Ping, Jinglei; Xi, Jin; Saven, Jeffery G.; Liu, Renyu; Charlie Johnson, A. T.

2015-01-01

Liquid-based applications of biomolecule-decorated field-effect transistors (FETs) range from biosensors to in vivo implants. A critical scientific challenge is to develop a quantitative understanding of the gating effect of charged biomolecules in ionic solution and how this influences the readout of the FETs. To address this issue, we fabricated protein-decorated graphene FETs and measured their electrical properties, specifically the shift in Dirac voltage, in solutions of varying ionic strength. We found excellent quantitative agreement with a model that accounts for both the graphene polarization charge and ionic screening of ions adsorbed on the graphene as well as charged amino acids associated with the immobilized protein. The technique and analysis presented here directly couple the charging status of bound biomolecules to readout of liquid-phase FETs fabricated with graphene or other two-dimensional materials. PMID:26626969

Deconstruction of Malaysian agro-wastes with inexpensive and bifunctional triethylammonium hydrogen sulfate ionic liquid

NASA Astrophysics Data System (ADS)

Zahari, S. M. Shahrul Nizan Shikh; Amin, Alia Thuraya Mohd; Halim, Nurdiyana Mohd; Rosli, Farah Amanina; Halim, Wan Ibrahim Thani Abd; Samsukamal, Nur Asyiqin; Sasithran, Bavitiraa; Ariffin, Nur'Alyaa Zainal; Azman, Hazeeq Hazwan; Hassan, Nur Hasyareeda; Othman, Zetty Shafiqa

2018-06-01

Ionic liquids (ILs) are known to be very effective at deconstructing biomass, but, they are typically 5-20 times more expensive than molecular solvents; this is a major impediment to the utilisation of ILs in biorefinery applications. In view of this, this paper is the first to report a preliminary study on the use of inexpensive and bifunctional triethylammonium hydrogen sulfate ionic liquid, [N2220][HSO4] IL, in deconstructing two Malaysian agro-wastes, oil palm empty fruit bunches (OPEFB) and coconut husk. The [N2220][HSO4] IL was synthesised via simple acid-base neutralisation route between two inexpensive precursors: sulfuric acid, H2SO4, and triethylamine, N222. The results of deconstruction of OPEFB and coconut husk under the applied conditions, IL/H2O (80/20 wt/wt) at 120 °C for 2 h, proved that the IL provided bifunctional action as: a Brønsted acid catalyst that hydrolysed chemical bonds linking carbohydrate-rich-material (cellulose and hemicellulose) and lignin fractions, and; a delignification agent that dissolved lignin, separating the biopolymer from the carbohydrate-rich-material. The outcomes of this study indicate that the deconstruction of Malaysian agro-wastes for isolating valuable biopolymers can be performed in a more economical and effective way using the [N2220][HSO4] IL.

Influence of the ionic liquid [C4mpy][Tf2N] on the structure of the miniprotein Trp-cage.

PubMed

Baker, Joseph L; Furbish, Jeffrey; Lindberg, Gerrick E

2015-11-01

We examine the effect of the ionic liquid [C4mpy][Tf2N] on the structure of the miniprotein Trp-cage and contrast these results with the behavior of Trp-cage in water. We find the ionic liquid has a dramatic effect on Trp-cage, though many similarities with aqueous Trp-cage are observed. We assess Trp-cage folding by monitoring root mean square deviation from the crystallographic structure, radius of gyration, proline cis/trans isomerization state, protein secondary structure, amino acid contact formation and distance, and native and non-native contact formation. Starting from an unfolded configuration, Trp-cage folds in water at 298 K in less than 500 ns of simulation, but has very little mobility in the ionic liquid at the same temperature, which can be ascribed to the higher ionic liquid viscosity. At 365 K, the mobility of the ionic liquid is increased and initial stages of Trp-cage folding are observed, however Trp-cage does not reach the native folded state in 2 μs of simulation in the ionic liquid. Therefore, in addition to conventional molecular dynamics, we also employ scaled molecular dynamics to expedite sampling, and we demonstrate that Trp-cage in the ionic liquid does closely approach the aqueous folded state. Interestingly, while the reduced mobility of the ionic liquid is found to restrict Trp-cage motion, the ionic liquid does facilitate proline cis/trans isomerization events that are not seen in our aqueous simulations. Copyright © 2015 Elsevier Inc. All rights reserved.

Acid-base characterization of 5-hydroxypyrazine-2-carboxylic acid and the role of ionic equilibria in the optimization of some process conditions for its biocatalytic production.

PubMed

Sak-Bosnar, M; Kovar, K

2005-10-01

This paper describes the use of potentiometric titration to determine the relevant acid-base properties of 5-hydroxypyrazine-2-carboxylic acid (5OH-PYCA), an important intermediate in the production of tuberculostatics. The data obtained were used for calculation of the dissociation constants of 5OH-PYCA. It was found that 5OH-PYCA dissociates in two steps, with the corresponding dissociation constants pK (a1)=3.42 and pK (a2)=7.96, designating 5OH-PYCA as a medium weak acid (1st step). The distribution diagram of dissociated species and the buffer-strength diagram of 5OH-PYCA provide useful information about its behaviour at different pH. The ionic equilibria data obtained can be used for selection of the optimum pH for biotransformation of pyrazine-2-carboxylic acid (PYCA) and for prediction of pH changes during the biotransformation. These data can also be used for selection of the optimum pH for precipitating 5OH-PYCA in downstream processing. All computations have been optimized by mathematical modelling using Solver.

Electroactive Ionic Soft Actuators with Monolithically Integrated Gold Nanocomposite Electrodes.

PubMed

Yan, Yunsong; Santaniello, Tommaso; Bettini, Luca Giacomo; Minnai, Chloé; Bellacicca, Andrea; Porotti, Riccardo; Denti, Ilaria; Faraone, Gabriele; Merlini, Marco; Lenardi, Cristina; Milani, Paolo

2017-06-01

Electroactive ionic gel/metal nanocomposites are produced by implanting supersonically accelerated neutral gold nanoparticles into a novel chemically crosslinked ion conductive soft polymer. The ionic gel consists of chemically crosslinked poly(acrylic acid) and polyacrylonitrile networks, blended with halloysite nanoclays and imidazolium-based ionic liquid. The material exhibits mechanical properties similar to that of elastomers (Young's modulus ≈ 0.35 MPa) together with high ionic conductivity. The fabrication of thin (≈100 nm thick) nanostructured compliant electrodes by means of supersonic cluster beam implantation (SCBI) does not significantly alter the mechanical properties of the soft polymer and provides controlled electrical properties and large surface area for ions storage. SCBI is cost effective and suitable for the scaleup manufacturing of electroactive soft actuators. This study reports the high-strain electromechanical actuation performance of the novel ionic gel/metal nanocomposites in a low-voltage regime (from 0.1 to 5 V), with long-term stability up to 76 000 cycles with no electrode delamination or deterioration. The observed behavior is due to both the intrinsic features of the ionic gel (elasticity and ionic transport capability) and the electrical and morphological features of the electrodes, providing low specific resistance (<100 Ω cm -2 ), high electrochemical capacitance (≈mF g -1 ), and minimal mechanical stress at the polymer/metal composite interface upon deformation. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

[Process and mechanism of plants in overcoming acid soil aluminum stress].

PubMed

Zhao, Tian-Long; Xie, Guang-Ning; Zhang, Xiao-Xia; Qiu, Lin-Quan; Wang, Na; Zhang, Su-Zhi

2013-10-01

Aluminum (Al) stress is one of the most important factors affecting the plant growth on acid soil. Currently, global soil acidification further intensifies the Al stress. Plants can detoxify Al via the chelation of ionic Al and organic acids to store the ionic Al in vacuoles and extrude it from roots. The Al extrusion is mainly performed by the membrane-localized anion channel proteins Al(3+)-activated malate transporter (ALMT) and multi-drug and toxin extrusion (MATE). The genes encoding ABC transporter and zinc-finger protein conferred plant Al tolerance have also been found. The identification of these Al-resistant genes makes it possible to increase the Al resistance of crop plants and enhance their production by the biological methods such as gene transformation and mark-associated breeding. The key problems needed to be solved and the possible directions in the researches of plant Al stress resistance were proposed.

Studies of bio-mimetic medium of ionic and non-ionic micelles by a simple charge transfer fluorescence probe N,N-dimethylaminonapthyl-(acrylo)-nitrile

NASA Astrophysics Data System (ADS)

Samanta, Anuva; Paul, Bijan Kumar; Guchhait, N.

2011-05-01

In this report we have studied micellization process of anionic, cationic and non-ionic surfactants using N,N-dimethylaminonapthyl-(acrylo)-nitrile (DMANAN) as an external fluorescence probe. Micropolarity, microviscosity, critical micellar concentration of these micelles based on steady state absorption and fluorescence and time resolved emission spectroscopy of the probe DMANAN show that the molecule resides in the micelle-water interface for ionic micelles and in the core for the non-ionic micelle. The effect of variation of pH of the micellar solution as well as fluorescence quenching measurements of DMANAN provide further support for the location of the probe in the micelles.

Empirical parameters for solvent acidity, basicity, dipolarity, and polarizability of the ionic liquids [BMIM][BF4] and [BMIM][PF6].

PubMed

del Valle, J C; García Blanco, F; Catalán, J

2015-04-02

The empirical solvent scales for polarizability (SP), dipolarity (SdP), acidity (SA), and basicity (SB) have been successfully used to interpret the solvatochromism of compounds dissolved in organic solvents and their solvent mixtures. Providing that the published solvatochromic parameters for the ionic liquids 1-(1-butyl)-3-methylimidazolium tetrafluoroborate, [BMIM][BF4] and 1-(1-butyl)-3-methylimidazolium hexafluorophosphate, [BMIM][PF6], are excessively widespread, their SP, SdP, SA, and SB values are measured herein at temperatures from 293 to 353 K. Four key points are emphasized herein: (i) the origin of the solvatochromic solvent scales--the gas phase, that is the absence of any medium perturbation--; (ii) the separation of the polarizability and dipolarity effects; (iii) the simplification of the probing process in order to obtain the solvatochromic parameters; and (iv) the SP, SdP, SA, and SB solvent scales can probe the polarizability, dipolarity, acidity, and basicity of ionic liquids as well as of organic solvents and water-organic solvent mixtures. From the multiparameter approach using the four pure solvent scales one can draw the conclusion that (a) the solvent influence of [BMIM][BF4] parallels that of formamide at 293 K, both of them miscible with water; (b) [BMIM][PF6] shows a set of solvatochromic parameters similar to that of chloroacetonitrile, both of them water insoluble; and (c) that the corresponding solvent acidity and basicity of the ionic liquids can be explained to a great extent from the cation species by comparing the empirical parameters of [BMIM](+) with those of the solvent 1-methylimidazole. The insolubility of [BMIM][PF6] in water as compared to [BMIM][BF4] is tentatively connected to some extent to the larger molar volume of the anion [PF6](-), and to the difference in basicity of [PF6](-) and [BF4](-).

Ionic Liquid Mediated Dispersion and Support of Functional Molecules on Cellulose Fibers for Stimuli-Responsive Chromic Paper Devices.

PubMed

Koga, Hirotaka; Nogi, Masaya; Isogai, Akira

2017-11-22

Functional molecules play a significant role in the development of high-performance composite materials. Functional molecules should be well dispersed (ideally dissolved) and supported within an easy-to-handle substrate to take full advantage of their functionality and ensure easy handling. However, simultaneously achieving the dissolution and support of functional molecules remains a challenge. Herein, we propose the combination of a nonvolatile ionic liquid and an easy-to-handle cellulose paper substrate for achieving this goal. First, the photochromic molecule, i.e., diarylethene, was dissolved in the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([bmim]NTf 2 ). Then, diarylethene/[bmim]NTf 2 was supported on cellulose fibers within the paper, through hydrogen bonding between [bmim] cations of the ionic liquid and the abundant hydroxyl groups of cellulose. The as-prepared paper composites exhibited reversible, rapid, uniform, and vivid coloration and bleaching upon ultraviolet and visible light irradiation. The photochromic performance was superior to that of the paper prepared in the absence of [bmim]NTf 2 . This concept could be applied to other functional molecules. For example, lithium perchlorate/[bmim] tetrafluoroborate supported within cellulose paper acted as a flexible electrolyte to provide a paper-based electrochromic device. These findings are expected to further the development of composite materials with high functionality and practicality.

Composite gel polymer electrolyte for lithium ion batteries

NASA Astrophysics Data System (ADS)

Naderi, Roya

Composite gel polymer electrolyte (CGPE) films, consisting of poly (vinylidene fluoride-hexafluoropropylene) (PVdF-HFP) as the membrane, DMF and PC as solvent and plasticizing agent, mixture of charge modified TiO2 and SiO 2 nano particles as ionic conductors, and LiClO4+LiPF 6 as lithium salts were fabricated. Following the work done by Li et al., CGPE was coated on an O2-plasma treated trilayer polypropylene-polyethylene-polypropylene membrane separator using solution casting technique in order to improve the adhesive properties of gel polymer electrolyte to the separator membrane and its respective ionic conductivity due to decreasing the bulk resistance. In acidic CGPE with, the mixture of acid treated TiO2 and neutral SiO2 nano particles played the role of the charge modified nano fillers with enhanced hydroxyl groups. Likely, the mixture of neutral TiO 2 nano particles with basic SiO2 prepared through the hydrolization of tetraethyl orthosilicate (TEOS) provided a more basic environment due to the residues of NH4OH (Ammonium hydroxide) catalyst. The O2 plasma treated separator was coated with the solution of PVDF-HFP: modified nano fillers: Organic solvents with the mixture ratio of 0.1:0.01:1. After the evaporation of the organic solvents, the dried coated separator was soaked in PC-LiClO4+LiPF6 in EC: DMC:DEC (4:2:4 in volume) solution (300% wt. of PVDF-HFP) to form the final CGPE. Lim et al. has reported the enhanced ionic conductivity of 9.78*10-5 Scm-1 in an acidic composite polystyrene-Al2O3 solid electrolyte system with compared to that of basic and neutral in which the ionic conductivity undergoes an ion hopping process in solid interface rather than a segmental movement of ions through the plasticized polymer chain . Half-cells with graphite anode and Li metal as reference electrode were then assembled and the electrochemical measurements and morphology examinations were successfully carried out. Half cells demonstrated a considerable change in their electrochemical performance upon the enhancement of acidic properties of the CGPE, gaining the reversible specific capacity of 314 mAh.g-1 in acidic CGPE vs. 247 mAh.g-1 in basic CGPE C/20 after 33 cycles. The CGPE exhibited submicron pore size while the ionic conductivities were in order of 10-3 and 10-5 Scm-1 with and without modified nano-fillers respectively.

Multi-Scale Simulation of High Energy Density Ionic Liquids

DTIC Science & Technology

2007-06-19

and simulation of ionic liquids (ILs). A polarizable model was developed to simulate ILs more accurately at the atomistic level. A multiscale coarse...propellant, 1- hydroxyethyl-4-amino-1, 2, 4-triazolium nitrate (HEATN), were studied with the all-atom polarizable model. The mechanism suggested for HEATN...with this AFOSR-supported project, a polarizable forcefield for the ionic liquids such as 1-ethyl-3-methylimidazolium nitrate (EMIM*/NO3-) was

Matrix-assisted laser desorption/ionization mass spectrometric analysis of aliphatic biodegradable photoluminescent polymers using new ionic liquid matrices.

PubMed

Serrano, Carlos A; Zhang, Yi; Yang, Jian; Schug, Kevin A

2011-05-15

In this study, two novel ionic liquid matrices (ILMs), N,N-diisopropylethylammonium 3-oxocoumarate and N,N-diisopropylethylammonium dihydroxymonooxoacetophenoate, were tested for the structural elucidation of recently developed aliphatic biodegradable polymers by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). The polymers, formed by a condensation reaction of three components, citric acid, octane diol, and an amino acid, are fluorescent, but the exact mechanism behind their luminescent properties has not been fully elucidated. In the original studies, which introduced the polymer class (J. Yang et al., Proc. Natl. Acad. Sci. USA 2009, 106, 10086-10091), a hyper-conjugated cyclic structure was proposed as the source for the photoluminescent behavior. With the use of the two new ILMs, we present evidence that supports the presence of the proposed cyclization product. In addition, the new ILMs, when compared with a previously established ILM, N,N-diisopropylethylammonium α-cyano-3-hydroxycinnimate, provided similar signal intensities and maintained similar spectral profiles. This research also established that the new ILMs provided good spot-to-spot reproducibility and high ionization efficiency compared with corresponding crystalline matrix preparations. Many polymer features revealed through the use of the ILMs could not be observed with crystalline matrices. Ultimately, the new ILMs highlighted the composition of the synthetic polymers, as well as the loss of water that was expected for the formation of the proposed cyclic structure on the polymer backbone. Copyright © 2011 John Wiley & Sons, Ltd.

Sensing of Double-Stranded DNA/RNA Secondary Structures by Water Soluble Homochiral Perylene Bisimide Dyes.

PubMed

Gershberg, Jana; Radić Stojković, Marijana; Škugor, Marko; Tomić, Sanja; Rehm, Thomas H; Rehm, Stefanie; Saha-Möller, Chantu R; Piantanida, Ivo; Würthner, Frank

2015-05-18

A broad series of homochiral perylene bisimide (PBI) dyes were synthesized that are appended with amino acids and cationic side chains at the imide positions. Self-assembly behavior of these ionic PBIs has been studied in aqueous media by UV/Vis spectroscopy, revealing formation of excitonically coupled H-type aggregates. The interactions of these ionic PBIs with different ds-DNA and ds-RNA have been explored by thermal denaturation, fluorimetric titration and circular dichroism (CD) experiments. These PBIs strongly stabilized ds-DNA/RNA against thermal denaturation as revealed by high melting temperatures of the formed PBI/polynucleotide complexes. Fluorimetric titrations showed that these PBIs bind to ds-DNA/RNA with high binding constants depending on the number of the positive charges in the side chains. Thus, spermine-containing PBIs with six positive charges each showed higher binding constants (logKs =9.2-9.8) than their dioxa analogues (logKs =6.5-7.9) having two positive charges each. Induced circular dichroism (ICD) of PBI assemblies created within DNA/RNA grooves was observed. These ICD profiles are strongly dependent on the steric demand of the chiral substituents of the amino acid units and the secondary structure of the DNA or RNA. The observed ICD effects can be explained by non-covalent binding of excitonically coupled PBI dimer aggregates into the minor groove of DNA and major groove of RNA which is further supported by molecular modeling studies. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Trace metals in the brain: allosteric modulators of ligand-gated receptor channels, the case of ATP-gated P2X receptors.

PubMed

Huidobro-Toro, J Pablo; Lorca, Ramón A; Coddou, Claudio

2008-03-01

Zinc and copper are indispensable trace metals for life with a recognized role as catalysts in enzyme actions. We now review evidence supporting the role of trace metals as novel allosteric modulators of ionotropic receptors: a new and fundamental physiological role for zinc and copper in neuronal and brain excitability. The review is focussed on ionotropic receptor channels including nucleotide receptors, in particular the P2X receptor family. Since zinc and copper are stored within synaptic vesicles in selected brain regions, and released to the synaptic cleft upon electrical nerve ending depolarization, it is plausible that zinc and copper reach concentrations in the synapse that profoundly affect ligand-gated ionic channels, including the ATP-gated currents of P2X receptors. The identification of key P2X receptor amino acids that act as ligands for trace metal coordination, carves the structural determinants underlying the allosteric nature of the trace metal modulation. The recognition that the identified key residues such as histidines, aspartic and glutamic acids or cysteines in the extracellular domain are different for each P2X receptor subtype and may be different for each metal, highlights the notion that each P2X receptor subtype evolved independent strategies for metal coordination, which form upon the proper three-dimensional folding of the receptor channels. The understanding of the molecular mechanism of allosteric modulation of ligand-operated ionic channels by trace metals is a new contribution to metallo-neurobiology.

Comparative study on copper leaching from waste printed circuit boards by typical ionic liquid acids.

PubMed

Chen, Mengjun; Huang, Jinxiu; Ogunseitan, Oladele A; Zhu, Nengming; Wang, Yan-min

2015-07-01

Waste printed circuit boards (WPCBs) are attracting increasing concerns because the recovery of its content of valuable metallic resources is hampered by the presence of hazardous substances. In this study, we used ionic liquids (IL) to leach copper from WPCBs. [BSO3HPy]OTf, [BSO3HMIm]OTf, [BSO4HPy]HSO4, [BSO4HMim]HSO4 and [MIm]HSO4 were selected. Factors that affect copper leaching rate were investigated in detail and their leaching kinetics were also examined with the comparison of [Bmim]HSO4. The results showed that all six IL acids could successfully leach copper out, with near 100% recovery. WPCB particle size and leaching time had similar influences on copper leaching performance, while IL acid concentration, hydrogen peroxide addition, solid to liquid ratio, temperature, showed different influences. Moreover, IL acid with HSO4(-) was more efficient than IL acid with CF3SO3(-). These six IL acids indicate a similar behavior with common inorganic acids, except temperature since copper leaching rate of some IL acids decreases with its increase. The results of leaching kinetics studies showed that diffusion plays a more important role than surface reaction, whereas copper leaching by inorganic acids is usually controlled by surface reaction. This innovation provides a new option for recovering valuable materials such as copper from WPCBs. Copyright © 2015 Elsevier Ltd. All rights reserved.

Perfluoroalkyl and polyfluoroalkyl substances in the lower atmosphere and surface waters of the Chinese Bohai Sea, Yellow Sea, and Yangtze River estuary.

PubMed

Zhao, Zhen; Tang, Jianhui; Mi, Lijie; Tian, Chongguo; Zhong, Guangcai; Zhang, Gan; Wang, Shaorui; Li, Qilu; Ebinghaus, Ralf; Xie, Zhiyong; Sun, Hongwen

2017-12-01

Polyfluoroalkyl and perfluoroalkyl substances (PFASs), in the forms of neutral polyfluoroalkyl substances in the gas phase of air and ionic perfluoroalkyl substances in the dissolved phase of surface water, were investigated during a sampling campaign in the Bohai Sea, Yellow Sea, and Yangtze River estuary in May 2012. In the gas phase, the concentrations of neutral ∑PFASs were within the range of 76-551pg/m 3 . Higher concentrations were observed in the South Yellow Sea. 8:2 fluorotelomer alcohol (FTOH) was the predominant compound as it accounted for 92%-95% of neutral ∑PFASs in all air samples. Air mass backward trajectory analysis indicated that neutral ∑PFASs came mainly from the coast of the Yellow Sea, including the Shandong, Jiangsu, and Zhejiang provinces of China, and the coastal region of South Korea. The fluxes of gas phase dry deposition were simulated for neutral PFASs, and neutral ∑PFASs fluxes varied from 0.37 to 2.3pg/m 2 /s. In the dissolved phase of the surface water, concentrations of ionic ∑PFASs ranged from 1.6 to 118ng/L, with the Bohai Sea exhibiting higher concentrations than both the Yellow Sea and the Yangtze River estuary. Perfluorooctanoic acid (PFOA) was the predominant compound accounting for 51%-90% of the ionic ∑PFAS concentrations. Releases from industrial and domestic activities as well as the semiclosed geographical conditions increased the level of ionic ∑PFASs in the Bohai Sea. The spatial distributions of perfluoroalkyl carboxylic acids (PFCAs) and perfluoroalkane sulfonic acids (PFSAs) were different significantly. The Laizhou Bay was the major source region of PFCAs and the Yangtze River estuary was the major source of PFSAs. Copyright © 2017 Elsevier B.V. All rights reserved.

Nanostructured protic ionic liquids retain nanoscale features in aqueous solution while precursor Brønsted acids and bases exhibit different behavior.

PubMed

Greaves, Tamar L; Kennedy, Danielle F; Weerawardena, Asoka; Tse, Nicholas M K; Kirby, Nigel; Drummond, Calum J

2011-03-10

Small- and wide-angle X-ray scattering (SWAXS) has been used to investigate the effect that water has on the nanoscale structure of protic ionic liquids (PILs) along with their precursor Brønsted acids and bases. The series of PILs consisted of primary, secondary, and tertiary alkylammonium cations in conjunction with formate, nitrate, or glycolate anions. Significant differences were observed for these systems. The nanoscale aggregates present in neat protic ionic liquids were shown to be stable in size on dilution to high concentrations of water, indicating that the water is localized in the ionic region and has little effect on the nonpolar domains. The Brønsted acid-water solutions did not display nanostructure at any water concentration. Primary amine Brønsted bases formed aggregates in water, which generally displayed characteristics of poorly structured microemulsions or a form of bicontinuous phase. Exceptions were butyl- and pentylamine with high water concentrations, for which the SWAXS patterns fitted well to the Teubner-Strey model for microemulsions. Brønsted base amines containing multiple alkyl chains or hydroxyl groups did not display nanostructure at any water concentration. IR spectroscopy was used to investigate the nature of water in the various solutions. For low PIL concentrations, the water was predominately present as bulk water for PIL molar fractions less than 0.4-0.5. At high PIL concentrations, in addition to the bulk water, there was a significant proportion of perturbed water, which is water influenced in some way by the cations and anions. The molecular state of the water in the studied amines was predominately present as bulk water, with smaller contributions from perturbed water than was seen in the PILs. © 2011 American Chemical Society

A facile synthesis of 3D NiFe2O4 nanospheres anchored on a novel ionic liquid modified reduced graphene oxide for electrochemical sensing of ledipasvir: Application to human pharmacokinetic study.

PubMed

El-Wekil, Mohamed M; Mahmoud, Ashraf M; Alkahtani, Saad A; Marzouk, Adel A; Ali, Ramadan

2018-06-30

Novel and sensitive electrochemical sensor was fabricated for the assay of anti-HCV ledipasvir (LEDV) in different matrices. The designed sensor was based on 3D spinel ferromagnetic NiFe 2 O 4 nanospheres and reduced graphene oxide (RGO) supported by morpholinium acid sulphate (MHS), as an ionic liquid (RGO/NSNiFe 2 O 4 /MHS). This sensor design was assigned to synergistically tailor the unique properties of nanostructured ferrites, RGO, and ionic liquid to maximize the sensor response. Electrode modification prevented aggregation of NiFe 2 O 4, increasing electroactive surface area and allowed remarkable electro-catalytic oxidation of LEDV with an enhanced oxidation response. Differential pulse voltammetry was used for detection LEDV in complex matrices whereas; cyclic voltammetry and other techniques were employed to characterize the developed sensor properties. All experimental factors regarding sensor fabrication and chemical sensing properties were carefully studied and optimized. Under the optimum conditions, the designated sensor displayed a wide linear range (0.4-350 ng mL -1 ) with LOD of 0.133 ng mL -1 . Additionally, the proposed sensor demonstrated good selectivity, stability and reproducibility, enabling the quantitative detection of LEDV in Harvoni ® tablets, human plasma and in a pharmacokinetic study. Our findings suggest that the developed sensor is a potential prototype material for fabrication of high-performance electrochemical sensors. Copyright © 2018 Elsevier B.V. All rights reserved.

Novel proton conducting polymer electrolytes based on polyparabanic acid doped with H 3PO 4 for high temperature fuel cell

NASA Astrophysics Data System (ADS)

Aihara, Yuichi; Sonai, Atsuo

Three novel proton conducting polymer electrolytes based on polyparabanic acid doped with H 3PO 4 were synthesized and their use in high temperature fuel cells characterized. The precursor polymers, PMD-Im, POD-Im and PDMDP-Im, were synthesized by cyclization polymerization of diisocynanates. After doping with H 3PO 4, the ionic conductivity and the thermal degradation were studied by using the AC impedance method and thermal gravimetric analysis, respectively. These membranes showed high ionic conductivity of the order of 10 -2 S cm -1 at 423 K with good thermal stability. Their application to fuel cells was demonstrated and polarization curves were obtained at 423 K were obtained without humidification.

Microwave-Assisted Syntheses in Recyclable Ionic Liquids: Photoresists Based on Renewable Resources

PubMed Central

Petit, Charlotte; Luef, Klaus P; Edler, Matthias; Griesser, Thomas; Kremsner, Jennifer M; Stadler, Alexander; Grassl, Bruno; Reynaud, Stéphanie; Wiesbrock, Frank

2015-01-01

The copoly(2-oxazoline) pNonOx80-stat-pDc=Ox20 can be synthesized from the cationic ring-opening copolymerization of 2-nonyl-2-oxazoline NonOx and 2-dec-9′-enyl-2-oxazoline Dc=Ox in the ionic liquid n-hexyl methylimidazolium tetrafluoroborate under microwave irradiation in 250 g/batch quantities. The polymer precipitates upon cooling, enabling easy recovery of the polymer and the ionic liquid. Both monomers can be obtained from fatty acids from renewable resources. pNonOx80-stat-pDc=Ox20 can be used as polymer in a photoresist (resolution of 1 μm) based on UV-induced thiol–ene reactions. PMID:26354027

Mixtures of amino-acid based ionic liquids and water.

PubMed

Chaban, Vitaly V; Fileti, Eudes Eterno

2015-09-01

New ionic liquids (ILs) involving increasing numbers of organic and inorganic ions are continuously being reported. We recently developed a new force field; in the present work, we applied that force field to investigate the structural properties of a few novel imidazolium-based ILs in aqueous mixtures via molecular dynamics (MD) simulations. Using cluster analysis, radial distribution functions, and spatial distribution functions, we argue that organic ions (imidazolium, deprotonated alanine, deprotonated methionine, deprotonated tryptophan) are well dispersed in aqueous media, irrespective of the IL content. Aqueous dispersions exhibit desirable properties for chemical engineering. The ILs exist as ion pairs in relatively dilute aqueous mixtures (10 mol%), while more concentrated mixtures feature a certain amount of larger ionic aggregates.

Solvation behaviour of L-leucine in aqueous ionic liquid at different temperatures: Volumetric approach

NASA Astrophysics Data System (ADS)

Sharma, Samriti; Sandarve, Sharma, Amit K.; Sharma, Meena

2018-05-01

For the investigation of interactions of L-leucine in aqueous solutions of an ionic liquid (1-butyl-3-methylimidazolium tetra fluoroborate [Bmim][BF4]) at atmospheric pressure over a temperature range of (293.15K to 313.16K), we use the volumetric approach. By using the density data we have calculated the apparent molar volume, VΦ, limiting apparent molar volume, V0Φ, the slope, Sv, partial molar volume of transfer, V0Φ,tr. The values of these acoustical parameters have been used for the interpretation of different interactions like hydrophilic-hydrophilic, hydrophilic-hydrophobic, ion hydrophilic, solute-solvent and solute-solute interactions in the amino acid and ionic liquid solutions.

"Nonsolvent" applications of ionic liquids in biotransformations and organocatalysis.

PubMed

Domínguez de María, Pablo

2008-01-01

The application of room-temperature ionic liquids (RTILs) as (co)solvents and/or reagents is well documented. However, RTILS also have "nonsolvent" applications in biotransformations and organocatalysis. Examples are the anchoring of substrates to RTILs; ionic-liquid-coated enzymes (ILCE) and enzyme-IL colyophilization; the construction of biocatalytic ternary reaction systems; the combination of enzymes, RTILs, membranes, and (bio)electrochemistry; and ionic-liquid-supported organocatalysts. These strategies provide more robust, more efficient, and more enantioselective bio- and organocatalysts with many practical applications. As shown herein, RTILs offer a wide range of promising alternatives to conventional chemistry.

Prediction of pH-Dependent Hydrophobic Profiles of Small Molecules from Miertus-Scrocco-Tomasi Continuum Solvation Calculations.

PubMed

Zamora, William J; Curutchet, Carles; Campanera, Josep M; Luque, F Javier

2017-10-26

Hydrophobicity is a key physicochemical descriptor used to understand the biological profile of (bio)organic compounds as well as a broad variety of biochemical, pharmacological, and toxicological processes. This property is estimated from the partition coefficient between aqueous and nonaqueous environments for neutral compounds (P N ) and corrected for the pH-dependence of ionizable compounds as the distribution coefficient (D). Here, we have extended the parametrization of the Miertus-Scrocco-Tomasi continuum solvation model in n-octanol to nitrogen-containing heterocyclic compounds, as they are present in many biologically relevant molecules (e.g., purines and pyrimidines bases, amino acids, and drugs), to obtain accurate log P N values for these molecules. This refinement also includes solvation calculations for ionic species in n-octanol with the aim of reproducing the experimental partition of ionic compounds (P I ). Finally, the suitability of different formalisms to estimate the distribution coefficient for a wide range of pH values has been examined for a set of small acidic and basic compounds. The results indicate that in general the simple pH-dependence model of the ionizable compound in water suffices to predict the partitioning at or around physiological pH. However, at extreme pH values, where ionic species are predominant, more elaborate models provide a better prediction of the n-octanol/water distribution coefficient, especially for amino acid analogues. Finally, the results also show that these formalisms are better suited to reproduce the experimental pH-dependent distribution curves of log D for both acidic and basic compounds as well as for amino acid analogues.

Thermodynamic characteristics of the acid-base equilibria of ethylenediamine- N, N'-diglutaric acid in aqueous solutions using calorimetric data

NASA Astrophysics Data System (ADS)

Gridchin, S. N.; Nikol'skii, V. M.

2017-10-01

The enthalpies of reaction of betaine group neutralization of ethylenediamine- N, N'-diglutaric acid (H4L) at 298.15 K and at different values of ionic strength of 0.1, 0.5, 1.0 (KNO3) is measured by direct calorimetry. The standard thermodynamic characteristics of the protolytic equilibria of H4L are calculated.

Catalytic Conversion of Carbohydrates to Levulinate Ester over Heteropolyanion-Based Ionic Liquids.

PubMed

Song, Changhua; Liu, Sijie; Peng, Xinwen; Long, Jinxing; Lou, Wenyong; Li, Xuehui

2016-12-08

An efficient one-pot approach for the production of levulinate ester from renewable carbohydrates is demonstrated over heteropolyanion-based ionic liquid (IL-POM) catalysts with alcohols as the promoters and solvents. The relationships between the structure, acidic strength, and solubility of the IL-POM in methanol and the catalytic performance were studied intensively. A cellulose conversion of 100 % could be achieved with a 71.4 % yield of methyl levulinate over the catalyst [PyPS] 3 PW 12 O 40 [PyPS=1-(3-sulfopropyl)pyridinium] at 150 °C for 5 h. This high efficiency is ascribed to the reasonably high activity of the ionic liquid (IL) catalyst and reaction coupling with rapid in situ esterification of the generated levulinic acid with the alcohol promoter, which allows the insolubility of cellulose encountered in biomass conversion to be overcome. Furthermore, the present process exhibits high feedstock adaptability for typical carbohydrates and handy catalyst recovery by a simple self-separation procedure through temperature control. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Adsorption of Eu(III) onto TiO2: effect of pH, concentration, ionic strength and soil fulvic acid.

PubMed

Tan, Xiaoli; Fang, Ming; Li, Jiaxing; Lu, Yi; Wang, Xiangke

2009-08-30

The effects of pH, initial Eu(III) concentration, ionic strength and fulvic acid (FA) on the adsorption of Eu(III) on TiO(2) are investigated by using batch techniques. The results indicate that the presence of FA strongly enhances the adsorption of Eu(III) on TiO(2) at low pH values. Besides, the adsorption of Eu(III) on TiO(2) is significantly dependent on pH values and independent of ionic strength. The adsorption of Eu(III) on TiO(2) is attributed to inner-sphere surface complexation. The diffuse layer model (DLM) is applied to simulate the adsorption data, and fits the experimental data well with the aid of FITEQL 3.2. X-ray photoelectron spectroscopy (XPS) is performed to study the species of Eu(III) adsorbed on the surfaces of TiO(2)/FA-TiO(2) hybrids at a molecular level, which suggest that FA act as "bridge" between Eu(III) and TiO(2) particles to enhance the ability to adsorb Eu(III) in solution.

Influence of the ionic liquid/gas surface on ionic liquid chemistry.

PubMed

Lovelock, Kevin R J

2012-04-21

Applications such as gas storage, gas separation, NP synthesis and supported ionic liquid phase catalysis depend upon the interaction of different species with the ionic liquid/gas surface. Consequently, these applications cannot proceed to the full extent of their potential without a profound understanding of the surface structure and properties. As a whole, this perspective contains more questions than answers, which demonstrates the current state of the field. Throughout this perspective, crucial questions are posed and a roadmap is proposed to answer these questions. A critical analysis is made of the field of ionic liquid/gas surface structure and properties, and a number of design rules are mined. The effects of ionic additives on the ionic liquid/gas surface structure are presented. A possible driving force for surface formation is discussed that has, to the best of my knowledge, not been postulated in the literature to date. This driving force suggests that for systems composed solely of ions, the rules for surface formation of dilute electrolytes do not apply. The interaction of neutral additives with the ionic liquid/gas surface is discussed. Particular attention is focussed upon H(2)O and CO(2), vital additives for many applications of ionic liquids. Correlations between ionic liquid/gas surface structure and properties, ionic liquid surfaces plus additives, and ionic liquid applications are given. This journal is © the Owner Societies 2012

Desulfurization of oxidized diesel using ionic liquids

NASA Astrophysics Data System (ADS)

Wilfred, Cecilia D.; Salleh, M. Zulhaziman M.; Mutalib, M. I. Abdul

2014-10-01

The extraction of oxidized sulfur compounds from diesel were carried out using ten types of ionic liquids consisting of different cation and anion i.e. 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazoium thiocyanate, 1-butyl-3-methylimidazoium dicyanamide, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazoliumhexafluorophosphate, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate, trioctylmethylammonium chloride, 1-propionitrile-3-butylimidazolium thiocyanate, 1-propionitrile-3-butylimidazolium dicyanamide and 1-butyl-6-methylquinolinium dicyanamide. The oxidation of diesel was successfully done using phosphotungstic acid as the catalyst, hydrogen peroxide (H2O2) as the oxidant and trioctylmethylammonium chloride as the phase transfer agent. The oxidation of diesel changes the sulfur compounds into sulfone which increases its polarity and enhances the ionic liquid's extraction performance. Result showed that ionic liquid [C4mquin][N(CN)2] performed the highest sulfur removal (91% at 1:5 diesel:IL ratio) compared to the others.

Reclamation of niobium compounds from ionic liquid electrochemical polishing of superconducting radio frequency cavities

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

Wixtrom, Alex I.; Buhler, Jessica E.; Reece, Charles E.

2013-06-01

Recent research has shown that choline chloride (vitamin B4)-based solutions can be used as a greener alternative to acid-based electrochemical polishing solutions. This study demonstrated a successful method for electrochemical deposition of niobium compounds onto the surface of copper substrates using a novel choline chloride-based ionic liquid. Niobium ions present in the ionic liquid solution were dissolved into the solution prior to deposition via electrochemical polishing of solid niobium. A black coating was clearly visible on the surface of the Cu following deposition. This coating was analyzed using scanning electron microscopy (SEM), electron dispersive X-ray spectroscopy (EDX), atomic force microscopymore » (AFM), and X-ray fluorescence spectroscopy (XRF). This ionic liquid-based electrochemical deposition method effectively recycles previously dissolved niobium from electrochemical polishing of superconducting radio frequency (SRF) cavities.« less

Synthesis and testing of hypergolic ionic liquids for chemical propulsion

NASA Astrophysics Data System (ADS)

Stovbun, S. V.; Shchegolikhin, A. N.; Usachev, S. V.; Khomik, S. V.; Medvedev, S. P.

2017-06-01

Synthesis of new highly energetic ionic liquids (ILs) is described, and their hypergolic ignition properties are tested. The synthesized ILs combine the advantages of conventional rocket propellants with the energy characteristics of acetylene derivatives. To this end, N-alkylated imidazoles (alkyl = ethyl, butyl) have been synthesized and alkylated with propargyl bromide. The desired ionic liquids have been produced by metathesis using Ag dicyanamide. Modified hypergolic drop tests with white fuming nitric acid have been performed for N-ethyl (IL-1) and N-butyl propargylimidazolium (IL-2) ionic liquids. In the modified drop tests, high-speed shadowgraph imaging is used to visualize the process, and the temperature rise due to ignition is monitored with a two-color photodetector. It is shown that the ignition delay is shorter for IL-1 as compared to IL-2. The ignition of IL-1 occurs in two stages, whereas the combustion of IL-2 proceeds smoothly without secondary flashes.

Polymeric micelles with ionic cores containing biodegradable cross-links for delivery of chemotherapeutic agents.

PubMed

Kim, Jong Oh; Sahay, Gaurav; Kabanov, Alexander V; Bronich, Tatiana K

2010-04-12

Novel functional polymeric nanocarriers with ionic cores containing biodegradable cross-links were developed for delivery of chemotherapeutic agents. Block ionomer complexes (BIC) of poly(ethylene oxide)-b-poly(methacylic acid) (PEO-b-PMA) and divalent metal cations (Ca(2+)) were utilized as templates. Disulfide bonds were introduced into the ionic cores by using cystamine as a biodegradable cross-linker. The resulting cross-linked micelles with disulfide bonds represented soft, hydrogel-like nanospheres and demonstrated a time-dependent degradation in the conditions mimicking the intracellular reducing environment. The ionic character of the cores allowed to achieve a very high level of doxorubicin (DOX) loading (50% w/w) into the cross-linked micelles. DOX-loaded degradable cross-linked micelles exhibited more potent cytotoxicity against human A2780 ovarian carcinoma cells as compared to micellar formulations without disulfide linkages. These novel biodegradable cross-linked micelles are expected to be attractive candidates for delivery of anticancer drugs.

Density and refractive index data of binary and ternary mixtures of imidazolium-based ionic liquids, n-hexane and organic compounds involved in the kinetic resolution of rac-2-pentanol.

PubMed

Montalbán, Mercedes G; Collado-González, Mar; Lozano-Pérez, A Abel; Baños, F Guillermo Díaz; Víllora, Gloria

2018-08-01

This data article is related to the subject of the research article "Extraction of Organic Compounds Involved in the Kinetic Resolution of rac-2-Pentanol from n-Hexane by Imidazolium-based Ionic Liquids: Liquid-Liquid Equilibrium" (Montalbán et al., 2018) [1]. It contains experimental data of density and refractive index of binary and ternary mixtures of imidazolium-based ionic liquids, n -hexane and organic compounds involved in the kinetic resolution of rac -2-pentanol ( rac -2-pentanol, vinyl butyrate, rac -2-pentyl butyrate or butyric acid) measured at 303.15 K and 1 atm. These data are presented as calibration curves which help to determine the composition of the ionic liquid-rich phase knowing its density or refractive index.

Descriptors for ions and ion-pairs for use in linear free energy relationships.

PubMed

Abraham, Michael H; Acree, William E

2016-01-22

The determination of Abraham descriptors for single ions is reviewed, and equations are given for the partition of single ions from water to a number of solvents. These ions include permanent anions and cations and ionic species such as carboxylic acid anions, phenoxide anions and protonated base cations. Descriptors for a large number of ions and ionic species are listed, and equations for the prediction of Abraham descriptors for ionic species are given. The application of descriptors for ions and ionic species to physicochemical processes is given; these are to water-solvent partitions, HPLC retention data, immobilised artificial membranes, the Finkelstein reaction and diffusion in water. Applications to biological processes include brain permeation, microsomal degradation of drugs, skin permeation and human intestinal absorption. The review concludes with a section on the determination of descriptors for ion-pairs. Copyright © 2015 Elsevier B.V. All rights reserved.

Sensing aggregation in highly turbid plasmonic and non-plasmonic colloidal suspensions

NASA Astrophysics Data System (ADS)

Ducay, Rey Nann Mark; Philip, Nathan; Boivin, Jordan; Judge, Patrick; Berberich, Jason; Scaffidi, Jonathan; Bali, Lalit; Bali, Samir

2015-05-01

We demonstrate a method for sensing the presence of aggregation in highly turbid aqueous suspensions of polystyrene and gold nanospheres. Aggregation is induced either by changing the pH or the ionic strength, by adding small, controlled amounts of an acid or base solution. The particle concentrations used are at least two orders of magnitude higher than previously reported. To the best of our knowledge, this is a first observation of aggregation in highly dense colloidal suspensions without any sample dilution or special sample preparation. We gratefully acknowledge support from the American Chemical Society Petroleum Research Fund and Miami University's Interdisciplinary Roundtable Fund. We also gratefully acknowledge experimental help from the Miami University Instrumentation Laboratory.

Morphologies of precise polyethylene-based acid copolymers and ionomers

NASA Astrophysics Data System (ADS)

Buitrago, C. Francisco

Acid copolymers and ionomers are polymers that contain a small fraction of covalently bound acidic or ionic groups, respectively. For the specific case of polyethylene (PE), acid and ionic pendants enhance many of the physical properties such as toughness, adhesion and rheological properties. These improved properties result from microphase separated aggregates of the polar pendants in the non-polar PE matrix. Despite the widespread industrial use of these materials, rigorous chemical structure---morphology---property relationships remain elusive due to the inevitable structural heterogeneities in the historically-available acid copolymers and ionomers. Recently, precise acid copolymers and ionomers were successfully synthesized by acyclic diene metathesis (ADMET) polymerization. These precise materials are linear, high molecular weight PEs with pendant acid or ionic functional groups separated by a precisely controlled number of carbon atoms. The morphologies of nine precise acid copolymers and eleven precise ionomers were investigated by X-ray scattering, solid-state 13C nuclear magnetic resonance (NMR) and differential scanning calorimetry (DSC). For comparison, the morphologies of linear PEs with pseudo-random placement of the pendant groups were also studied. Previous studies of precise copolymers with acrylic acid (AA) found that the microstructural precision produces a new morphology in which PE crystals drive the acid aggregates into layers perpendicular to the chain axes and presumably at the interface between crystalline and amorphous phases. In this dissertation, a second new morphology for acid copolymers is identified in which the aggregates arrange on cubic lattices. The fist report of a cubic morphology was observed at room and elevated temperatures for a copolymer functionalized with two phosphonic acid (PA) groups on every 21st carbon atom. The cubic lattice has been identified as face-centered cubic (FCC). Overall, three morphology types have been identified for precise acid copolymers and ionomers at room temperature: (1) liquid-like order of aggregates dispersed throughout an amorphous PE matrix, (2) one-dimensional long-range order of aggregates in layers coexisting with PE crystals, and (3) three-dimensional periodicity of aggregates in cubic lattices in a PE matrix featuring defective packing. The liquid-like morphology is a result of high content of acid or ionic substituents deterring PE crystallinity due to steric hindrance. The layered morphology occurs when the content of pendants is low and the PE segments are long enough to crystallize. The cubic morphologies occur in precise copolymers with geminal substitution of phosphonic acid (PA) groups and long, flexible PE segments. At temperatures above the thermal transitions of the PE matrix, all but one material present a liquid-like morphology. Those conditions are ideal to study the evolution of the interaggregate spacing (d*) in X-ray scattering as a function of PE segment length between pendants, pendant type and pendant architecture (specifically, mono or geminal substitution). Also at elevated temperatures, the morphologies of precise acrylic acid (AA) copolymers and ionomers were investigated further via atomistic molecular dynamics (MD) simulations. The simulations complement X-ray scattering by providing real space visualization of the aggregates, demonstrating the occurrence of isolated, string-like and even percolated aggregate structures. This is the first dissertation completely devoted to the morphology of precise acid copolymers and precise ionomers. The complete analysis of the morphologies in these novel materials provides new insights into the shapes of aggregates in acid copolymers and ionomers in general. A key aspect of this thesis is the complementary use of experimental and simulation methods to unlock a wealth of new understanding.

Feasibility of a Supporting-Salt-Free Nonaqueous Redox Flow Battery Utilizing Ionic Active Materials.

PubMed

Milshtein, Jarrod D; Fisher, Sydney L; Breault, Tanya M; Thompson, Levi T; Brushett, Fikile R

2017-05-09

Nonaqueous redox flow batteries (NAqRFBs) are promising devices for grid-scale energy storage, but high projected prices could limit commercial prospects. One route to reduced prices is to minimize or eliminate the expensive supporting salts typically employed in NAqRFBs. Herein, the feasibility of a flow cell operating in the absence of supporting salt by utilizing ionic active species is demonstrated. These ionic species have high conductivities in acetonitrile (12-19 mS cm -1 ) and cycle at 20 mA cm -2 with energy efficiencies (>75 %) comparable to those of state-of-the-art NAqRFBs employing high concentrations of supporting salt. A chemistry-agnostic techno-economic analysis highlights the possible cost savings of minimizing salt content in a NAqRFB. This work offers the first demonstration of a NAqRFB operating without supporting salt. The associated design principles can guide the development of future active species and could make NAqRFBs competitive with their aqueous counterparts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Exploring the ionic strength effects on the photochemical degradation of pyruvic acid in atmospheric deliquescent aerosol particles

NASA Astrophysics Data System (ADS)

Mekic, Majda; Brigante, Marcello; Vione, Davide; Gligorovski, Sasho

2018-07-01

There is increasing evidence that aqueous-phase atmospheric chemistry is an important source of secondary organic aerosols (SOA), but the related processes are currently not adequately represented in atmospheric chemistry models. Here we show that the absorption spectrum of pyruvic acid (PA) exhibits both an increase of the absorption intensity and a red shift of 13 nm while going from a dilute aqueous phase to a solution containing the inert salt sodium perchlorate (5M NaClO4). If this phenomenon turns out to be more general, many compounds that do not absorb actinic light in clouds and fog could become light absorbers at elevated salt concentrations in aerosol deliquescent particles. Compared to the direct photolysis of PA in dilute aqueous solution, the photolysis rate is increased by three times at high ionic strength (5M NaClO4). Such a considerable enhancement can be rationalized in the framework of the Debye-McAulay approach for reactions of ionic + neutral (or neutral + neutral) species, considering that the PA direct photolysis likely involves interaction between the photogenerated triplet state and water. This is, to our knowledge, the first report of a significant effect of the ionic strength on the rate of an atmospheric photochemical reaction. The phenomenon has important implications for the fate of PA and, potentially, of other organic compounds in atmospheric aerosol deliquescent particles.

Interfacial Shear Strength and Adhesive Behavior of Silk Ionomer Surfaces.

PubMed

Kim, Sunghan; Geryak, Ren D; Zhang, Shuaidi; Ma, Ruilong; Calabrese, Rossella; Kaplan, David L; Tsukruk, Vladimir V

2017-09-11

The interfacial shear strength between different layers in multilayered structures of layer-by-layer (LbL) microcapsules is a crucial mechanical property to ensure their robustness. In this work, we investigated the interfacial shear strength of modified silk fibroin ionomers utilized in LbL shells, an ionic-cationic pair with complementary ionic pairing, (SF)-poly-l-glutamic acid (Glu) and SF-poly-l-lysine (Lys), and a complementary pair with partially screened Coulombic interactions due to the presence of poly(ethylene glycol) (PEG) segments and SF-Glu/SF-Lys[PEG] pair. Shearing and adhesive behavior between these silk ionomer surfaces in the swollen state were probed at different spatial scales and pressure ranges by using functionalized atomic force microscopy (AFM) tips as well as functionalized colloidal probes. The results show that both approaches were consistent in analyzing the interfacial shear strength of LbL silk ionomers at different spatial scales from a nanoscale to a fraction of a micron. Surprisingly, the interfacial shear strength between SF-Glu and SF-Lys[PEG] pair with partially screened ionic pairing was greater than the interfacial shear strength of the SF-Glu and SF-Lys pair with a high density of complementary ionic groups. The difference in interfacial shear strength and adhesive strength is suggested to be predominantly facilitated by the interlayer hydrogen bonding of complementary amino acids and overlap of highly swollen PEG segments.

Ion chromatography with the indirect ultraviolet detection of alkali metal ions and ammonium using imidazolium ionic liquid as ultraviolet absorption reagent and eluent.

PubMed

Liu, Yong-Qiang; Yu, Hong

2016-08-01

Indirect ultraviolet detection was conducted in ultraviolet-absorption-agent-added mobile phase to complete the detection of the absence of ultraviolet absorption functional group in analytes. Compared with precolumn derivatization or postcolumn derivatization, this method can be widely used, has the advantages of simple operation and good linear relationship. Chromatographic separation of Li(+) , Na(+) , K(+) , and NH4 (+) was performed on a carboxylic acid base cation exchange column using imidazolium ionic liquid/acid/organic solvent as the mobile phase, in which imidazolium ionic liquids acted as ultraviolet absorption reagent and eluting agent. The retention behaviors of four kinds of cations are discussed, and the mechanism of separation and detection are described. The main factors influencing the separation and detection were the background ultraviolet absorption reagent and the concentration of hydrogen ion in the ion chromatography-indirect ultraviolet detection. The successful separation and detection of Li(+) , Na(+) , K(+) , and NH4 (+) within 13 min was achieved using the selected chromatographic conditions, and the detection limits (S/N = 3) were 0.02, 0.11, 0.30, and 0.06 mg/L, respectively. A new separation and analysis method of alkali metal ions and ammonium by ion chromatography with indirect ultraviolet detection method was developed, and the application range of ionic liquid was expanded. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Transformation of CuO Nanoparticles in the Aquatic Environment: Influence of pH, Electrolytes and Natural Organic Matter

PubMed Central

Peng, Cheng; Shen, Chensi; Zheng, Siyuan; Yang, Weiling; Hu, Hang; Liu, Jianshe; Shi, Jiyan

2017-01-01

Many studies have shown the effect of solution chemistry on the environmental behavior of metal-based nanoparticles (NPs), except CuO NPs. Here, we investigated the agglomeration, sedimentation, dissolution, and speciation of CuO NPs by varying pH, ionic strength, ionic valence, and natural organic matter (NOM). The results showed that as the pH moved away from 6, the size of CuO agglomerates decreased, along with the enhanced NP suspension stabilization, due to the increase of electrostatic repulsive force. Increasing ionic strength and valence intensified the agglomeration and sedimentation of CuO NPs because of the compression of electrical double layers. The presence of humic acid and citric acid enhanced the dispersion and stabilization of CuO NP suspension, but l-cysteine showed a different impact. Decreasing pH, increasing ionic strength and all NOM improved the dissolution of CuO NPs, but the divalent electrolyte (CaCl2) inhibited the Cu2+ release from CuO NPs compared to the monovalent electrolyte (NaCl). In addition, X-ray absorption near edge structure (XANES) analysis demonstrated that the presence of l-cysteine transformed more than 30% of CuO NPs to Cu(I)-cysteine by coordinating with thiol group. This study can give us an in-depth understanding on the environmental behavior and fate of CuO NPs in the aquatic environment. PMID:29036921

The magic of aqueous solutions of ionic liquids: ionic liquids as a powerful class of catanionic hydrotropes†

PubMed Central

Cláudio, Ana Filipa M.; Neves, Márcia C.; Shimizu, Karina; Canongia Lopes, José N.; Freire, Mara G.; Coutinho, João A. P.

2015-01-01

Hydrotropes are compounds able to enhance the solubility of hydrophobic substances in aqueous media and therefore are widely used in the formulation of drugs, cleaning and personal care products. In this work, it is shown that ionic liquids are a new class of powerful catanionic hydrotropes where both the cation and the anion synergistically contribute to increase the solubility of biomolecules in water. The effects of the ionic liquid chemical structures, their concentration and the temperature on the solubility of two model biomolecules, vanillin and gallic acid were evaluated and compared with the performance of conventional hydrotropes. The solubility of these two biomolecules was studied in the entire composition range, from pure water to pure ionic liquids, and an increase in the solubility of up to 40-fold was observed, confirming the potential of ionic liquids to act as hydrotropes. Using dynamic light scattering, NMR and molecular dynamics simulations, it was possible to infer that the enhanced solubility of the biomolecule in the IL aqueous solutions is related to the formation of ionic-liquid–biomolecules aggregates. Finally, it was demonstrated that hydrotropy induced by ionic liquids can be used to recover solutes from aqueous media by precipitation, simply by using water as an anti-solvent. The results reported here have a significant impact on the understanding of the role of ionic liquid aqueous solutions in the extraction of value-added compounds from biomass as well as in the design of novel processes for their recovery from aqueous media. PMID:26379471

Catalytic ignition of ionic liquids for propellant applications.

PubMed

Shamshina, Julia L; Smiglak, Marcin; Drab, David M; Parker, T Gannon; Dykes, H Waite H; Di Salvo, Roberto; Reich, Alton J; Rogers, Robin D

2010-12-21

In this proof of concept study, the ionic liquids, 2-hydroxyethylhydrazinium nitrate and 2-hydroxyethylhydrazinium dinitrate, ignited on contact with preheated Shell 405 (iridium supported on alumina) catalyst and energetically decomposed with no additional ignition source, suggesting a possible route to hydrazine replacements.

Acid and alkali doped PBI electrolyte in electrochemical system

NASA Astrophysics Data System (ADS)

Xing, Baozhong

In this work the conductivity of blank PBI membrane, acid doped PBI and alkaline doped PBI was systematically studied. A new methodology for sorption kinetics study in electrolyte solution has been established by monitoring the conductivity change during the sorption process. The model of the doping process and mechanism of conductivity are proposed. The performance of PBI (doped under optimum conditions) in fuel cell as PEM was evaluated. The experimental results show that the blank PBI in acid solution is an ionic insulator. It clarified the long time confusion in this area. The acid doped PBI membrane is an ionic conductor. The conductivity increases with the concentration of the acid solution. In high concentration acid solution, the conductivity increases with the type of acid in the order: H2SO 4 > H3PO4 > HClO4 > HNO3 > HCl. The kinetics of the doping process was studied, by a continuous method. The ionic conductivity mechanism was established. The PBI membranes doped with H2SO4 and H3PO4 exhibit better performance than NafionRTM. The doped FBI has more resistance to CO poison. 3% CO in H2 has little effect on the H3PO 4 doped PBI membrane at 185°C. The conductivity of the alkali doped PBI membrane changes with the concentration of the alkaline solution and the type of the alkalis. The conductivity has a maximum in KOH and NaOH solution. The maximum conductivity in KOH is higher than in NaOH and LiOH. It is about 5 times of that of NafionRTM in alkaline solution. The two-step sorption process in alkaline solution was observed. The first step is the permeation process of the alkalis in the PBI membrane. The permeation is the results of diffusion and interaction. It is concluded that the permeation process is controlled by the rate of interaction between the alkali and PBI molecule. The second step is the relaxation process in the membrane. This step contributes more to the conductivity for the membrane than the first step. The ionic conductivity mechanism was established. In solution the cations and OH- all participate in the transport of current. It is the OH- that breaks the bonds between PBI molecules and enables the cations pass through the membrane. The performance of alkali doped PBI (doped under optimum conditions) in fuel cell as PEM is as good as NafionRTM.

Charge ordering in ionic fluids mediate repulsive surface interactions

NASA Astrophysics Data System (ADS)

Dasbiswas, Kinjal; Ludwig, Nicholas B.; Zhang, Hao; Talapin, Dmitri; Vaikuntanathan, Suri

Recent experiments on ionic fluids, such as surface force measurements in organic ionic liquids and the observation of colloidal stability in inorganic molten salts, suggest the presence of long-ranged repulsive forces. These cannot be explained within the classical Debye-Hückel theory for dilute electrolytes. We argue that such repulsive interactions can arise from long-range (several nm) charge density oscillations induced by a surface that preferentially binds one of the ionic species in an ionic fluid. We present a continuum theory that accounts for such charge layering based on a frustrated Ising model that incorporates both long-range Coulombic and short-range steric interactions. The mean-field analytic treatment qualitatively matches results from molecular simulations. A careful analysis of the ionic correlation functions arising from such charge ordering may also explain the long electrostatic screening lengths observed in various ionic fluids and their non-monotonic dependence on the electrolyte concentration. We acknowledge the University of Chicago for support.

Investigation into the Depth of Cure of Resin-Modified Glass-Ionomer Restorative Materials

DTIC Science & Technology

2006-08-01

al?2 studied the acid/base reaction of glass ionomer cements using Raman spectroscopy and confirmed the necessity of water availability for the acid...exchange layer." In the ion-exchange layer, Wilson et al.48 postulated the formation of an ionic bond between the polyacrylic acid and the hydroxyapatite ...investigators further detailed the interaction between the polyalkenoic acids and hydroxyapatite in a later report?’ The bonding of RMGI to dentin was

Properties of an ionic liquid-tolerant Bacillus amyloliquefaciens CMW1 and its extracellular protease.

PubMed

Kurata, Atsushi; Senoo, Humiya; Ikeda, Yasuyuki; Kaida, Hideaki; Matsuhara, Chiaki; Kishimoto, Noriaki

2016-07-01

An ionic liquid-tolerant bacterium, Bacillus amyloliquefaciens CMW1, was isolated from a Japanese fermented soybean paste. Strain CMW1 grew in the presence of 10 % (v/v) 1-butyl-3-methylimidazolium chloride ([BMIM]Cl), a commonly used ionic liquid. Additionally, strain CMW1 grew adequately in the presence of the hydrophilic ionic liquids 10 % (v/v) 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([EMIM]CF3SO3) or 2.5 % (v/v) 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([BMIM]CF3SO3). Strain CMW1 produced an extracellular protease (BapIL) in the culture medium. BapIL was stable in the presence of 80 % (v/v) ionic liquids, [EMIM]CF3SO3, [BMIM]Cl, [BMIM]CF3SO3, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, and functioned in 10 % (v/v) these ionic liquids. BapIL was stable at pH 4.0-12.6 or in 4004 mM NaCl solution, and exhibited activity in the presence of 50 % (v/v) hydrophilic or hydrophobic organic solvents. BapIL was completely inhibited by 1 mM PMSF and partially by 5 mM EDTA. BapIL belongs to the true subtilisins according to analysis of the deduced amino acid sequence. We showed that BapIL from the ionic liquid-tolerant B. amyloliquefaciens CMW1 exhibited tolerance to ionic liquid and halo, alkaline, and organic solvents.

Amino acids as possible alternative nitrogen source for growth of Euglena gracilis Z in life support systems

NASA Astrophysics Data System (ADS)

Richter, P. R.; Liu, Y.; An, Y.; Li, X.; Nasir, A.; Strauch, S. M.; Becker, I.; Krüger, J.; Schuster, M.; Ntefidou, M.; Daiker, V.; Haag, F. W. M.; Aiach, A.; Lebert, M.

2015-01-01

In recent times Euglena gracilis Z was employed as primary producer in closed environmental life-support system (CELSS), e.g. in space research. The photosynthetic unicellular flagellate is not capable of utilizing nitrate, nitrite, and urea as nitrogen source. Therefore, ammonium is supplied as an N-source in the lab (provided as diammonium-dihydrogenphosphate, (NH4)2HPO4) to E. gracilis cultures. While nitrate exerts low toxicity to organisms, ammonium is harmful for many aquatic organisms especially, at high pH-values, which causes the ionic NH+4 (low toxicity) to be partially transformed into the highly toxic ammonia, NH3. In earlier reports, Euglena gracilis was described to grow with various amino acids as sole N-source. Our aim was to investigate alternatives for (NH4)2HPO4 as N-source with lower toxicity for organisms co-cultivated with Euglena in a CELSS. The growth kinetics of Euglena gracilis cultures was determined in the presence of different amino acids (glycine, glutamine, glutamic acid, leucine, and threonine). In addition, uptake of those amino acids by the cells was measured. Cell growth in the presence of glycine and glutamine was quite comparable to the growth in (NH4)2HPO4 containing cultures while a delay in growth was observed in the presence of leucine and threonine. Unlike, aforementioned amino acids glutamate consumption was very poor. Cell density and glutamate concentration were almost unaltered throughout the experiment and the culture reached the stationary phase within 8 days. The data are compared with earlier studies in which utilization of amino acids in Euglena gracilis was investigated. All tested amino acids (glutamate with limitations) were found to have the potential of being an alternative N-source for Euglena gracilis. Hence, these amino acids can be used as a non-toxic surrogate for (NH4)2HPO4.

Amino acids as possible alternative nitrogen source for growth of Euglena gracilis Z in life support systems.

PubMed

Richter, P R; Liu, Y; An, Y; Li, X; Nasir, A; Strauch, S M; Becker, I; Krüger, J; Schuster, M; Ntefidou, M; Daiker, V; Haag, F W M; Aiach, A; Lebert, M

2015-01-01

In recent times Euglena gracilis Z was employed as primary producer in closed environmental life-support system (CELSS), e.g. in space research. The photosynthetic unicellular flagellate is not capable of utilizing nitrate, nitrite, and urea as nitrogen source. Therefore, ammonium is supplied as an N-source in the lab (provided as diammonium-dihydrogenphosphate, (NH4)2HPO4) to E. gracilis cultures. While nitrate exerts low toxicity to organisms, ammonium is harmful for many aquatic organisms especially, at high pH-values, which causes the ionic NH4+ (low toxicity) to be partially transformed into the highly toxic ammonia, NH3. In earlier reports, Euglena gracilis was described to grow with various amino acids as sole N-source. Our aim was to investigate alternatives for (NH4)2HPO4 as N-source with lower toxicity for organisms co-cultivated with Euglena in a CELSS. The growth kinetics of Euglena gracilis cultures was determined in the presence of different amino acids (glycine, glutamine, glutamic acid, leucine, and threonine). In addition, uptake of those amino acids by the cells was measured. Cell growth in the presence of glycine and glutamine was quite comparable to the growth in (NH4)2HPO4 containing cultures while a delay in growth was observed in the presence of leucine and threonine. Unlike, aforementioned amino acids glutamate consumption was very poor. Cell density and glutamate concentration were almost unaltered throughout the experiment and the culture reached the stationary phase within 8 days. The data are compared with earlier studies in which utilization of amino acids in Euglena gracilis was investigated. All tested amino acids (glutamate with limitations) were found to have the potential of being an alternative N-source for Euglena gracilis. Hence, these amino acids can be used as a non-toxic surrogate for (NH4)2HPO4. Copyright © 2014 The Committee on Space Research (COSPAR). Published by Elsevier Ltd. All rights reserved.

Theoretical investigation of the interaction between aromatic sulfur compounds and [BMIM](+)[FeCl4](-) ionic liquid in desulfurization: A novel charge transfer mechanism.

PubMed

Li, Hongping; Zhu, Wenshuai; Chang, Yonghui; Jiang, Wei; Zhang, Ming; Yin, Sheng; Xia, Jiexiang; Li, Huaming

2015-06-01

In this work, interaction nature between a group of aromatic sulfur compounds and [BMIM](+)[FeCl4](-) have been investigated by density functional theory (DFT). A coordination structure is found to be critical to the mechanism of extractive desulfurization. Interaction energy and extractive selectivity follow the order: thiophene (TH)

Synthesis and characterization of novel chiral ionic liquids and investigation of their enantiomeric recognition properties.

PubMed

Bwambok, David K; Marwani, Hadi M; Fernand, Vivian E; Fakayode, Sayo O; Lowry, Mark; Negulescu, Ioan; Strongin, Robert M; Warner, Isiah M

2008-02-01

We report the synthesis and characterization of amino acid ester based chiral ionic liquids, derived from L- and D-alanine tert butyl ester chloride. The synthesis was accomplished via an anion metathesis reaction between commercially available L- and D-alanine tert butyl ester chloride using a variety of counterions such as lithium bis (trifluoromethane) sulfonimide, silver nitrate, silver lactate, and silver tetrafluoroborate. Both enantiomeric forms were obtained as confirmed by bands of opposite sign in the circular dichroism spectra. The L- and D-alanine tert butyl ester bis (trifluoromethane) sulfonimide were obtained as liquids at room temperature and intriguingly exhibited the highest thermal stability (up to 263 degrees C). In addition, the ionic liquids demonstrated enantiomeric recognition ability as evidenced by splitting of racemic Mosher's sodium salt signal using a liquid state (19)F nuclear magnetic resonance (NMR) and fluorescence spectroscopy. The L- and D-alanine tert butyl ester chloride resulted in solid salts with nitrate, lactate, and tetrafluoroborate anions. This illustrates the previously observed tunability of ionic liquid synthesis, resulting in ionic liquids of varying properties as a function of varying the anion.

A novel and simple strategy for simultaneous determination of dopamine, uric acid and ascorbic acid based on the stacked graphene platelet nanofibers/ionic liquids/chitosan modified electrode.

PubMed

Niu, Xiuli; Yang, Wu; Guo, Hao; Ren, Jie; Yang, Fusheng; Gao, Jinzhang

2012-09-15

A promising electrochemical sensor for simultaneous determination of dopamine (DA), uric acid (UA) and ascorbic acid (AA) was fabricated based on the stacked graphene platelet nanofibers (SGNF)/ionic liquid (IL)/chitosan (CS) modified electrode. The SGNF/IL/CS modified electrode possessed excellent electrocatalytic activity towards the oxidation of DA, UA and AA with obvious reduction of over-potential and increased peak current, and the separations of oxidation peak potentials of DA-UA, DA-AA, and UA-AA were of 151, 213 and 364 mV, respectively. Under the optimum conditions, the linear range for the detection of DA, UA and AA were 0.05-240, 0.12-260, and 30-350 μM with the lowest detection limits of 0.05, 0.10 and 14.8 μM for DA, UA and AA, respectively. In addition, the electrochemical sensor showed high sensitivity, excellent selectivity, reproducibility and long-term stability. Copyright © 2012 Elsevier B.V. All rights reserved.

Acidic Zeolite L as a Highly Efficient Catalyst for Dehydration of Fructose to 5-Hydroxymethylfurfural in Ionic Liquid.

PubMed

Ma, Zhongsen; Hu, Hualei; Sun, Zhongqiang; Fang, Wenting; Zhang, Jian; Yang, Longfei; Zhang, Yajie; Wang, Lei

2017-04-22

Zeolite L was synthesized by the hydrothermal method and post-treated by NH 4 exchange to adjust its acidity. The samples were systematic characterized by various techniques including XRD, X-ray fluorescence spectroscopy, N 2 adsorption-desorption, scanning electron microscopy, pyridine IR spectroscopy, and NH 3 temperature-programmed desorption. The results demonstrated that the NH 4 -exchange post-treatment increased the surface area, micropore volume, and acidity of zeolite L. The catalytic performance of the samples was tested in the dehydration of fructose to 5-hydroxymethylfurfural (HMF) in ionic liquid (1-butyl-3-methylimidazolium bromide, [bmim]Br). 99.1 % yield of HMF was obtained when the KL-80 °C-1 h sample (KL zeolite treated with 1 m NH 4 NO 3 solution at 80 °C for 1 h) was used. The high efficiency could be attributed to the appropriate acid properties of the catalyst. The zeolite catalyst could be reused four times without significant decrease in activity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bond-valence methods for pKa prediction. II. Bond-valence, electrostatic, molecular geometry, and solvation effects

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

Bickmore, Barry R.; Rosso, Kevin M.; Tadanier, Christopher J.

2006-08-15

In a previous contribution, we outlined a method for predicting (hydr)oxy-acid and oxide surface acidity constants based on three main factors: bond valence, Me?O bond ionicity, and molecular shape. Here electrostatics calculations and ab initio molecular dynamics simulations are used to qualitatively show that Me?O bond ionicity controls the extent to which the electrostatic work of proton removal departs from ideality, bond valence controls the extent of solvation of individual functional groups, and bond valence and molecular shape controls local dielectric response. These results are consistent with our model of acidity, but completely at odds with other methods of predictingmore » acidity constants for use in multisite complexation models. In particular, our ab initio molecular dynamics simulations of solvated monomers clearly indicate that hydrogen bonding between (hydr)oxo-groups and water molecules adjusts to obey the valence sum rule, rather than maintaining a fixed valence based on the coordination of the oxygen atom as predicted by the standard MUSIC model.« less

Comparison of ionic and non-ionic drug release from multi-membrane spherical aerogels.

PubMed

Veronovski, Anja; Knez, Zeljko; Novak, Zoran

2013-09-15

The presented research was oriented towards the preparation of dry biodegradable alginate aerogels with multi-membranes using a multi-step sol-gel process with potential applications as carriers during oral drug delivery. First alginate spherical hydrogels were formed in CaCl2 or BaCl2 solutions by ionic cross-linking. These cores were further immersed into alginate sodium solution, filtered through a sieve, and dropped into the salt solution again. Multi-membrane hydrogels were obtained by repeating the above process. They were further converted into aerogels by supercritical drying. The effect of the number of membranes was investigated regarding the loading and release of the model drugs nicotinic acid and theophylline. Moreover, the efficiencies of Ba(2+) and Ca(2+) metal ions for forming tridimensional networks that retain and extend drug release were also investigated. Nicotinic acid release was prolonged by adding membranes around the core and using Ca(2+) for cross-linking. However, retarded theophylline release was only obtained by using Ba(2+) for cross-linking. Namely, by increasing the number of membranes and BaCl2 concentration drug release became linear versus time in all studied cases. In the case of nicotinic acid loading increased by adding membranes around the core, however, for theophylline the opposite results were obtained due to the different nature of the model drugs. Copyright © 2013 Elsevier B.V. All rights reserved.

IgG1 adsorption to siliconized glass vials-influence of pH, ionic strength, and nonionic surfactants.

PubMed

Höger, Kerstin; Mathes, Johannes; Frieß, Wolfgang

2015-01-01

In this study, the adsorption of an IgG1 antibody to siliconized vials was investigated with focus on the formulation parameters pH, ionic strength, and nonionic surfactants. Electrophoretic mobility measurements were performed to investigate the charge characteristics of protein and siliconized glass particles at different pH values. Calculation of the electrokinetic charge density allowed further insight into the energetic conditions in the protein-sorbent interface. Maximum adsorption of IgG1 was found at acidic pH values and could be correlated with energetically favorable minimal ion incorporation into the interface. The importance of electrostatic interactions for IgG1 adsorption at acidic pH values was also confirmed by the efficient adsorption reduction at decreased solution ionic strength. A second adsorption maximum around the pI of the protein was assigned to hydrophobic interactions with the siliconized surface. Addition of the nonionic surfactants poloxamer 188 or polysorbate 80 resulted in almost complete suppression of adsorption at pH 7.2, and a strong but less efficient effect at pH 4 on siliconized glass vials. This adsorption suppression was much less pronounced on borosilicate glass vials. From these results, it can be concluded that electrostatic interactions contribute substantially to IgG1 adsorption to siliconized glass vials especially at acidic formulation pH. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

Surface science and model catalysis with ionic liquid-modified materials.

PubMed

Steinrück, H-P; Libuda, J; Wasserscheid, P; Cremer, T; Kolbeck, C; Laurin, M; Maier, F; Sobota, M; Schulz, P S; Stark, M

2011-06-17

Materials making use of thin ionic liquid (IL) films as support-modifying functional layer open up a variety of new possibilities in heterogeneous catalysis, which range from the tailoring of gas-surface interactions to the immobilization of molecularly defined reactive sites. The present report reviews recent progress towards an understanding of "supported ionic liquid phase (SILP)" and "solid catalysts with ionic liquid layer (SCILL)" materials at the microscopic level, using a surface science and model catalysis type of approach. Thin film IL systems can be prepared not only ex-situ, but also in-situ under ultrahigh vacuum (UHV) conditions using atomically well-defined surfaces as substrates, for example by physical vapor deposition (PVD). Due to their low vapor pressure, these systems can be studied in UHV using the full spectrum of surface science techniques. We discuss general strategies and considerations of this approach and exemplify the information available from complementary methods, specifically photoelectron spectroscopy and surface vibrational spectroscopy. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rare Earth Extraction from NdFeB Magnet Using a Closed-Loop Acid Process.

PubMed

Kitagawa, Jiro; Uemura, Ryohei

2017-08-14

There is considerable interest in extraction of rare earth elements from NdFeB magnets to enable recycling of these elements. In practical extraction methods using wet processes, the acid waste solution discharge is a problem that must be resolved to reduce the environmental impact of the process. Here, we present an encouraging demonstration of rare earth element extraction from a NdFeB magnet using a closed-loop hydrochloric acid (HCl)-based process. The extraction method is based on corrosion of the magnet in a pretreatment stage and a subsequent ionic liquid technique for Fe extraction from the HCl solution. The rare earth elements are then precipitated using oxalic acid. Triple extraction has been conducted and the recovery ratio of the rare earth elements from the solution is approximately 50% for each extraction process, as compared to almost 100% recovery when using a one-shot extraction process without the ionic liquid but with sufficient oxalic acid. Despite its reduced extraction efficiency, the proposed method with its small number of procedures at almost room temperature is still highly advantageous in terms of both cost and environmental friendliness. This study represents an initial step towards realization of a closed-loop acid process for recycling of rare earth elements.

Disinfection of Spacecraft Potable Water Systems by Passivation with Ionic Silver

NASA Technical Reports Server (NTRS)

Birmele, Michele N.; McCoy, LaShelle e.; Roberts, Michael S.

2011-01-01

Microbial growth is common on wetted surfaces in spacecraft environmental control and life support systems despite the use of chemical and physical disinfection methods. Advanced control technologies are needed to limit microorganisms and increase the reliability of life support systems required for long-duration human missions. Silver ions and compounds are widely used as antimicrobial agents for medical applications and continue to be used as a residual biocide in some spacecraft water systems. The National Aeronautics and Space Administration (NASA) has identified silver fluoride for use in the potable water system on the next generation spacecraft. Due to ionic interactions between silver fluoride in solution and wetted metallic surfaces, ionic silver is rapidly depleted from solution and loses its antimicrobial efficacy over time. This report describes research to prolong the antimicrobial efficacy of ionic silver by maintaining its solubility. Three types of metal coupons (lnconel 718, Stainless Steel 316, and Titanium 6AI-4V) used in spacecraft potable water systems were exposed to either a continuous flow of water amended with 0.4 mg/L ionic silver fluoride or to a static, pre-treatment passivation in 50 mg/L ionic silver fluoride with or without a surface oxidation pre-treatment. Coupons were then challenged in a high-shear, CDC bioreactor (BioSurface Technologies) by exposure to six bacteria previously isolated from spacecraft potable water systems. Continuous exposure to 0.4 mg/L ionic silver over the course of 24 hours during the flow phase resulted in a >7-log reduction. The residual effect of a 24-hour passivation treatment in 50 mg/L of ionic silver resulted in a >3-log reduction, whereas a two-week treatment resulted in a >4-log reduction. Results indicate that 0.4 mg/L ionic silver is an effective biocide against many bacteria and that a prepassivation of metal surfaces with silver can provide additional microbial control.

Controlling adsorption and passivation properties of bovine serum albumin on silica surfaces by ionic strength modulation and cross-linking.

PubMed

Park, Jae Hyeon; Sut, Tun Naw; Jackman, Joshua A; Ferhan, Abdul Rahim; Yoon, Bo Kyeong; Cho, Nam-Joon

2017-03-29

Understanding the physicochemical factors that influence protein adsorption onto solid supports holds wide relevance for fundamental insights into protein structure and function as well as for applications such as surface passivation. Ionic strength is a key parameter that influences protein adsorption, although how its modulation might be utilized to prepare well-coated protein adlayers remains to be explored. Herein, we investigated how ionic strength can be utilized to control the adsorption and passivation properties of bovine serum albumin (BSA) on silica surfaces. As protein stability in solution can influence adsorption kinetics, the size distribution and secondary structure of proteins in solution were first characterized by dynamic light scattering (DLS), nanoparticle tracking analysis (NTA), and circular dichroism (CD) spectroscopy. A non-monotonic correlation between ionic strength and protein aggregation was observed and attributed to colloidal agglomeration, while the primarily α-helical character of the protein in solution was maintained in all cases. Quartz crystal microbalance-dissipation (QCM-D) experiments were then conducted in order to track protein adsorption onto silica surfaces as a function of ionic strength, and the measurement responses indicated that total protein uptake at saturation coverage is lower with increasing ionic strength. In turn, the QCM-D data and the corresponding Voigt-Voinova model analysis support that the surface area per bound protein molecule is greater with increasing ionic strength. While higher protein uptake under lower ionic strengths by itself did not result in greater surface passivation under subsequent physiologically relevant conditions, the treatment of adsorbed protein layers with a gluteraldehyde cross-linking agent stabilized the bound protein in this case and significantly improved surface passivation. Collectively, our findings demonstrate that ionic strength modulation influences BSA adsorption uptake on account of protein spreading and can be utilized in conjunction with covalent cross-linking strategies to prepare well-coated protein adlayers for improved surface passivation.

Parasitic Currents Caused by Different Ionic and Electronic Conductivities in Fuel Cell Anodes.

PubMed

Schalenbach, Maximilian; Zillgitt, Marcel; Maier, Wiebke; Stolten, Detlef

2015-07-29

The electrodes in fuel cells simultaneously realize electric and ionic conductivity. In the case of acidic polymer electrolytes, the electrodes are typically made of composites of carbon-supported catalyst and Nafion polymer electrolyte binder. In this study, the interaction of the proton conduction, the electron conduction, and the electrochemical hydrogen conversion in such composite electrode materials was examined. Exposed to a hydrogen atmosphere, these composites displayed up to 10-fold smaller resistivities for the proton conduction than that of Nafion membranes. This effect was ascribed to the simultaneously occurring electrochemical hydrogen oxidation and evolution inside the composite samples, which are driven by different proton and electron resistivities. The parasitic electrochemical currents resulting were postulated to occur in the anode of fuel cells with polymer, solid oxide, or liquid alkaline electrolytes, when the ohmic drop of the ion conduction in the anode is higher with the anodic kinetic overvoltage (as illustrated in the graphical abstract). In this case, the parasitic electrochemical currents increase the anodic kinetic overpotential and the ohmic drop in the anode. Thinner fuel cell anodes with smaller ohmic drops for the ion conduction may reduce the parasitic electrochemical currents.

ISOTOPE FRACTIONATION PROCESS

DOEpatents

Clewett, G.H.; Lee, DeW.A.

1958-05-20

A new method is described for isotopic enrichment of uranium. It has been found that when an aqueous acidic solution of ionic tetravalent uraniunn is contacted with chelate complexed tetravalent uranium, the U/sup 238/ preferentially concentrates in the complexed phase while U/sup 235/ concentrates in the ionic phase. The effect is enhanced when the chelate compound is water insoluble and is dissolved in a water-immiscible organic solvent. Cupferron is one of a number of sultable complexing agents, and chloroform is a suitable organic solvent.

Polymer gel electrolytes for application in aluminum deposition and rechargeable aluminum ion batteries

DOE PAGES

Sun, Xiao -Guang; Fang, Youxing; Jiang, Xueguang; ...

2015-10-22

Polymer gel electrolyte using AlCl3 complexed acrylamide as functional monomer and ionic liquids based on acidic mixture of 1-ethyl-3-methylimidazolium chloride (EMImCl) and AlCl 3 as plasticizer has been successfully prepared for the first time by free radical polymerization. Aluminum deposition is successfully obtained with a polymer gel membrane contianing 80 wt% ionic liquid. As a result, the polymer gel membranes are also good candidates for rechargeable aluminum ion batteries.

Ionic Attachment as a Feasible Approach to Heterogenizing Anionic Solution Catalysts. The Carbonylation of Methanol,

DTIC Science & Technology

1980-08-01

carbonylation of methanol to acetic acid reaction is well suited for a demonstration of the feasibility and value of ionically binding a catalyst to a...approximate doubling of the reaction rate. This result suggests that a liquid flow system design in which there is a large catalyst to methanol ratio could...Heterogenizing Anionic Solution Catalysts . The Carbonylation of Methanol by Russell S. Drago, Eric D. Nyberg, Anton El A’mma and Alan Zombeck ABSTRACT -’Few

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

Socha, Aaron; Singh, Seema; Simmons, Blake A.

Methods and compositions are provided for synthesizing ionic liquids from lignin derived compounds comprising: contacting a starting material comprising lignin with a depolymerization agent to depolymerize the lignin and form a mixture of aldehyde containing compounds; contacting the mixture of aldehyde containing compounds with an amine under conditions suitable to convert the mixture of aldehyde containing compounds to a mixture of amine containing compounds; and contacting the mixture of amine containing compounds with an acid under conditions suitable to form an ammonium salt, thereby preparing the ionic liquid.

Novel Proton Conducting Solid Bio-polymer Electrolytes Based on Carboxymethyl Cellulose Doped with Oleic Acid and Plasticized with Glycerol

NASA Astrophysics Data System (ADS)

Chai, M. N.; Isa, M. I. N.

2016-06-01

The plasticized solid bio-polymer electrolytes (SBEs) system has been formed by introducing glycerol (Gly) as the plasticizer into the carboxymethyl cellulose (CMC) doped with oleic acid (OA) via solution casting techniques. The ionic conductivity of the plasticized SBEs has been studied using Electrical Impedance Spectroscopy. The highest conductivity achieved is 1.64 × 10-4 S cm-1 for system containing 40 wt. % of glycerol. FTIR deconvolution technique had shown that the conductivity of CMC-OA-Gly SBEs is primarily influenced by the number density of mobile ions. Transference number measurement has shown that the cation diffusion coefficient and ionic mobility is higher than anion which proved the plasticized polymer system is a proton conductor.

Introducing biobased ionic liquids as the nonaqueous media for enzymatic synthesis of phosphatidylserine.

PubMed

Bi, Yan-Hong; Duan, Zhang-Qun; Li, Xiang-Qian; Wang, Zhao-Yu; Zhao, Xi-Rong

2015-02-11

Biobased ionic liquids with cholinium as the cation and amino acids as the anions, which could be prepared from renewable biomaterials by simple neutralization reactions, have recently been described as promising and green solvents. Herein, they were successfully used as the reaction media for enzyme-mediated transphosphatidylation of phosphatidylcholine with l-serine for phosphatidylserine synthesis for the first time. Our results indicated that the highest phosphatidylserine yield of 86.5% was achieved. Moreover, 75% original activity of the enzyme was maintained after being used for 10 batches. The present work could be considered an alternative enzymatic strategy for preparing phosphatidylserine. Additionally, the excellent results make the biobased ionic liquids more promising candidates for use as environmentally friendly solvents in biocatalysis fields.

Preparation and physical properties of (PVA)0.7(NaBr)0.3(H3PO4)xM solid acid membrane for phosphoric acid – Fuel cells

PubMed Central

Ahmad, F.; Sheha, E.

2012-01-01

A solid acid membranes based on poly (vinyl alcohol) (PVA), sodium bromide (NaBr) and phosphoric acid (H3PO4) were prepared by a solution casting method. The morphological, IR, electrical and optical properties of the (PVA)0.7(NaBr)0.3(H3PO4)xM solid acid membranes where x = 0.00, 0.85, 1.7, 3.4, 5.1 M were investigated. The variation of film morphology was examined by scanning electron microscopy (SEM) studies. FTIR spectroscopy has been used to characterize the structure of polymer and confirms the complexation of phosphoric acid with host polymeric matrix. The temperature dependent nature of ionic conductivity and the impedance of the polymer electrolytes were determined along with the associated activation energy. The ionic conductivity at room temperature was found to be strongly depends on the H3PO4 concentration which it has been achieved to be of the order 4.3 × 10−3 S/cm at ambient temperature. Optical measurements showed a decrease in optical band gap and an increase in band tail width with the increase of phosphoric acid. The data shows that the (PVA)0.7(NaBr)0.3(H3PO4)xM solid acid membrane is promising for intermediate temperature phosphoric acid fuel cell applications. PMID:25685413

Nanomechanics of layer-by-layer polyelectrolyte complexes: a manifestation of ionic cross-links and fixed charges.

PubMed

Han, Biao; Chery, Daphney R; Yin, Jie; Lu, X Lucas; Lee, Daeyeon; Han, Lin

2016-01-28

This study investigates the roles of two distinct features of ionically cross-linked polyelectrolyte networks - ionic cross-links and fixed charges - in determining their nanomechanical properties. The layer-by-layer assembled poly(allylamine hydrochloride)/poly(acrylic acid) (PAH/PAA) network is used as the model material. The densities of ionic cross-links and fixed charges are modulated through solution pH and ionic strength (IS), and the swelling ratio, elastic and viscoelastic properties are quantified via an array of atomic force microscopy (AFM)-based nanomechanical tools. The roles of ionic cross-links are underscored by the distinctive elastic and viscoelastic nanomechanical characters observed here. First, as ionic cross-links are highly sensitive to solution conditions, the instantaneous modulus, E0, exhibits orders-of-magnitude changes upon pH- and IS-governed swelling, distinctive from the rubber elasticity prediction based on permanent covalent cross-links. Second, ionic cross-links can break and self-re-form, and this mechanism dominates force relaxation of PAH/PAA under a constant indentation depth. In most states, the degree of relaxation is >90%, independent of ionic cross-link density. The importance of fixed charges is highlighted by the unexpectedly more elastic nature of the network despite low ionic cross-link density at pH 2.0, IS 0.01 M. Here, the complex is a net charged, loosely cross-linked, where the degree of relaxation is attenuated to ≈50% due to increased elastic contribution arising from fixed charge-induced Donnan osmotic pressure. In addition, this study develops a new method for quantifying the thickness of highly swollen polymer hydrogel films. It also underscores important technical considerations when performing nanomechanical tests on highly rate-dependent polymer hydrogel networks. These results provide new insights into the nanomechanical characters of ionic polyelectrolyte complexes, and lay the ground for further investigation of their unique time-dependent properties.

Protic ammonium carboxylate ionic liquids: insight into structure, dynamics and thermophysical properties by alkyl group functionalization.

PubMed

Reddy, Th Dhileep N; Mallik, Bhabani S

2017-04-19

This study is aimed at characterising the structure, dynamics and thermophysical properties of five alkylammonium carboxylate ionic liquids (ILs) from classical molecular dynamics simulations. The structural features of these ILs were characterised by calculating the site-site radial distribution functions, g(r), spatial distribution functions and structure factors. The structural properties demonstrate that ILs show greater interaction between cations and anions when alkyl chain length increases on the cation or anion. In all ILs, spatial distribution functions show that the anion is close to the acidic hydrogen atoms of the ammonium cation. We determined the role of alkyl group functionalization of the charged entities, cations and anions, in the dynamical behavior and the transport coefficients of this family of ionic liquids. The dynamics of ILs are described by studying the mean square displacement (MSD) of the centres of mass of the ions, diffusion coefficients, ionic conductivities and hydrogen bonds as well as residence dynamics. The diffusion coefficients and ionic conductivity decrease with an increase in the size of the cation or anion. The effect of alkyl chain length on ionic conductivity calculated in this article is consistent with the findings of other experimental studies. Hydrogen bond lifetimes and residence times along with structure factors were also calculated, and are related to alkyl chain length.

Choline-Based Amino Acid ILs-Collagen Interaction: Enunciating Its Role in Stabilization/Destabilization Phenomena.

PubMed

Tarannum, Aafiya; Rao, J Raghava; Fathima, N Nishad

2018-01-25

Given the potential of productive interaction between choline-based amino acid ionic liquids (CAAILs) and collagen, we investigated the role of four CAAILs, viz., choline serinate, threoninate, lysinate, and phenylalaninate, and the changes mediated by them in the structure of collagen at different hierarchical orderings, that is, at molecular and fibrillar levels. The rheological, dielectric behavior and the secondary structural changes signify the alteration in the triple helical structure of collagen at higher concentrations of CAAILs. A marginal swelling and slight decrease in the thermal stability of rat tail tendon collagen fibers were observed for choline serinate and threoninate, albeit distortions in banding patterns were noticed for choline lysinate and phenylalaninate, suggesting chaotropicity of the ions at the fibrillar level. This signifies the changes in the hydrogen-bonding environment of collagen with increasing concentrations of CAAILs, which could be due to competitive hydrogen bonding between the carbonyl group of amino acid ionic liquids and the hydroxyl groups of collagen.

Multiple functions of the crustacean gill: osmotic/ionic regulation, acid-base balance, ammonia excretion, and bioaccumulation of toxic metals

PubMed Central

Henry, Raymond P.; Lucu, Čedomil; Onken, Horst; Weihrauch, Dirk

2012-01-01

The crustacean gill is a multi-functional organ, and it is the site of a number of physiological processes, including ion transport, which is the basis for hemolymph osmoregulation; acid-base balance; and ammonia excretion. The gill is also the site by which many toxic metals are taken up by aquatic crustaceans, and thus it plays an important role in the toxicology of these species. This review provides a comprehensive overview of the ecology, physiology, biochemistry, and molecular biology of the mechanisms of osmotic and ionic regulation performed by the gill. The current concepts of the mechanisms of ion transport, the structural, biochemical, and molecular bases of systemic physiology, and the history of their development are discussed. The relationship between branchial ion transport and hemolymph acid-base regulation is also treated. In addition, the mechanisms of ammonia transport and excretion across the gill are discussed. And finally, the toxicology of heavy metal accumulation via the gill is reviewed in detail. PMID:23162474

Unraveling the Structural Modifications in Lignin of Arundo donax Linn. during Acid-Enhanced Ionic Liquid Pretreatment.

PubMed

You, Tingting; Zhang, Liming; Guo, Siqin; Shao, Lupeng; Xu, Feng

2015-12-23

Solid acid-enhanced ionic liquid (IL) pretreatment is of paramount importance for boosting the yield of sugars from biomass cost-effectively and environmentally friendly. To unravel the chemical and supramolecular structural changes of lignin after pretreatment, IL-acid lignin (ILAL) and subsequent residual cellulolytic enzyme lignin (RCEL) were isolated from Arundo donax Linn. The structural features were compared with those of the corresponding milled wood lignin (MWL). Results indicated that the pretreatment caused loss of β-O-4', β-β', β-1' linkages and formation of condensed structures in lignin. A preferential breakdown of G-type lignin may have occurred, evidenced by an increased S/G ratio revealed by 2D HSQC NMR analysis. It was determined that the depolymerization of β-O-4' linkage, lignin recondensation, and cleavage of ferulate-lignin ether linkages took place. Moreover, a simulation module was first developed to define morphological changes in lignin based on AFM and TEM analyses. Briefly, tree branch like aggregates was destroyed to monodisperse particles.

Porous polycarbene-bearing membrane actuator for ultrasensitive weak-acid detection and real-time chemical reaction monitoring.

PubMed

Sun, Jian-Ke; Zhang, Weiyi; Guterman, Ryan; Lin, Hui-Juan; Yuan, Jiayin

2018-04-30

Soft actuators with integration of ultrasensitivity and capability of simultaneous interaction with multiple stimuli through an entire event ask for a high level of structure complexity, adaptability, and/or multi-responsiveness, which is a great challenge. Here, we develop a porous polycarbene-bearing membrane actuator built up from ionic complexation between a poly(ionic liquid) and trimesic acid (TA). The actuator features two concurrent structure gradients, i.e., an electrostatic complexation (EC) degree and a density distribution of a carbene-NH 3 adduct (CNA) along the membrane cross-section. The membrane actuator performs the highest sensitivity among the state-of-the-art soft proton actuators toward acetic acid at 10 -6  mol L -1 (M) level in aqueous media. Through competing actuation of the two gradients, it is capable of monitoring an entire process of proton-involved chemical reactions that comprise multiple stimuli and operational steps. The present achievement constitutes a significant step toward real-life application of soft actuators in chemical sensing and reaction technology.

Light scattering measurements supporting helical structures for chromatin in solution.

PubMed

Campbell, A M; Cotter, R I; Pardon, J F

1978-05-01

Laser light scattering measurements have been made on a series of polynucleosomes containing from 50 to 150 nucleosomes. Radii of gyration have been determined as a function of polynucleosome length for different ionic strength solutions. The results suggest that at low ionic strength the chromatin adopts a loosely helical structure rather than a random coil. The helix becomes more regular on increasing the ionic strength, the dimension resembling those proposed by Finch and Klug for their solenoid model.

Self-Healing Behavior of Ethylene-Based Ionomers

NASA Technical Reports Server (NTRS)

Kalista, Stephen J., Jr.; Ward, Thomas C.; Oyetunji, Zainab

2004-01-01

The self-healing behavior of poly(ethylene-co-methacrylic acid) (EMAA)-based ionomers holds tremendous potential for use in a wide variety of unique applications. However, to effectively utilize this self-healing behavior and to design novel materials which possess this ability, the mechanism by which they heal must first be understood ionomers are a class of polymers that can be described as copolymers containing less than 15 mol% ionic content whereby the bulk properties are governed by ionic interactions within the polymer. These ionic groups aggregate into discrete regions known as multiplets which overlap forming clusters that act as physical cross-links profoundly influencing the bulk physical properties. These clusters possess an order-disorder transition (T(sub i)) where the clustered regions may rearrange themselves given time and stimuli. Recognizing the strong influence of these ionic regions on other well understood ionomer properties, their role in self-heating behavior will be assessed. The self-healing behavior is observed following projectile puncture. It has been suggested that during impact energy is passed to the ionomer material, heating it to the melt state. After penetration, it is proposed that the ionic regions maintain their attractions and flow together patching the hole. Thus, the importance of this ionic character and is unique interaction must be established. This will be accomplished through examination of materials with varying ionic content and through the analysis of the T(sub i). The specific ionomer systems examined include a number of ethylene-based materials. Materials of varying ionic content, including the non-ionic base copolymers, will be examined by peel tests, projectile impact and DSC analysis. The information will also be compared with some basic data on LDPE material.

[Characteristics of the aggregative state of the substrate in the reaction of 5-lipoxygenase oxidation of linoleic acid].

PubMed

Butovich, I A; Kharchenko, O V; Paboka, Iu N; Kazachkov, M G

2001-01-01

5-lipoxygenase (EC 1.13.11.12) oxidizes polyunsaturated fatty acids by molecular oxygen. The enzyme acts in close contact with the cell membranes, which main components are ionic and non-ionic lipids. In order to investigate the kinetic parameters of 5-lipoxygenase reaction in vitro, extremely hydrophobic fatty acid substrate (linoleic acid) should be solubilized in the reaction mixture. We used Lubrol PX ("Sigma" Chem. Co), as a non-ionic detergent consisted of oligoethylene glycol and fatty alcohol. Linoleic acid and Lubrol PX formed mixed micelles thus solubilizing the fatty acid substrate in a buffer with appropriate pH. We have studied the sizes and shapes of mixed micelles Lubrol PX/linoleic acid (aggregates type 1) and Lubrol PX/linoleic acid/SDS (aggregates type 2; SDS was an effective activator of potato tuber 5-lipoxygenase) by means of gel-filtration and laser light scattering techniques. The parameters under investigation were molecular weights, Stocks radii and shapes of the mixed micelles. The average molecular weights and Stocks radii of the mixed micelles type 1 determined by mean of gel-filtration on Sephadex G-200 were 95,142 +/- 5184 Da and 3.45 +/- 0.11 nm, respectively. The same parameters for the mixed micelles type 2 were 73,694 +/- 893 Da and 3.02 +/- 0.02 nm, respectively. The strong similarity in physicochemical parameters for both types of mixed micelles indicated that SDS did not influence the size and shape of mixed micelles of Lubrol PX and linoleic acid. The activatory action of SDS on potato tuber lipoxygenase may be a result of electrostatic effect or direct participation of SDS in enzymatic catalysis. The laser light scattering technique allowed to determine two main fraction of particles in type 1 system with hydrodynamic diameters 2.6 and 5.7 nm and relative contribution to light scattering 13 and 87%, respectively. The particles with d = 5.7 nm were interpreted as the mixed micelles. The particles with d = 2.6 nm were interpreted as isolated molecules of Lubrol PX, linoleic acid and (or) their premicellar aggregates. The data obtained are to be used in creation of reliable physical and mathematical models of 5-lipoxygenase.

The Amateur Scientist: Funny Things Happen When Drops of Oil or Other Substances Are Placed on Water.

ERIC Educational Resources Information Center

Walker, Jearl

1983-01-01

Discusses solubility interactions of various oils placed on the surface of water and other liquids, explained using the basic forces of gravity, electrical attraction, and quantum mechanics (non-mathematical). Hydrogen and ionic bonding between oleic acid/water is analyzed. An experiment to determine physical properties of the oleic acid molecule…

Advanced Supported Liquid Membranes for Carbon Dioxide Control in Extravehicular Activity Applications

NASA Technical Reports Server (NTRS)

Gleason, Kevin J. (Inventor); Cowley, Scott W. (Inventor); Wickham, David T. (Inventor)

2015-01-01

There is disclosed a portable life support system with a component for removal of at least one selected gas. In an embodiment, the system includes a supported liquid membrane having a first side and a second side in opposition to one another, the first side configured for disposition toward an astronaut and the second side configured for disposition toward a vacuum atmosphere. The system further includes an ionic liquid disposed between the first side and the second side of the supported liquid membrane, the ionic liquid configured for removal of at least one selected gas from a region housing the astronaut adjacent the first side of the supported liquid membrane to the vacuum atmosphere adjacent the second side of the supported liquid membrane. Other embodiments are also disclosed.

Simulated Moving Bed Chromatography: Separation and Recovery of Sugars and Ionic Liquid from Biomass Hydrolysates

PubMed Central

Caes, Benjamin R.; Van Oosbree, Thomas R.; Lu, Fachuang; Ralph, John; Maravelias, Christos T.

2015-01-01

Simulated moving bed chromatography, a continuous separation method, enables the nearly quantitative recovery of sugar products and ionic liquid solvent from chemical hydrolysates of biomass. The ensuing sugars support microbial growth, and the residual lignin from the process is intact. PMID:23939991

Lidocaine self-sacrificially improves the skin permeation of the acidic and poorly water-soluble drug etodolac via its transformation into an ionic liquid.

PubMed

Miwa, Yasushi; Hamamoto, Hidetoshi; Ishida, Tatsuhiro

2016-05-01

Poor transdermal penetration of active pharmaceutical ingredients (APIs) impairs both bioavailability and therapeutic benefits and is a major challenge in the development of transdermal drug delivery systems. Here, we transformed a poorly water-soluble drug, etodolac, into an ionic liquid in order to improve its hydrophobicity, hydrophilicity and skin permeability. The ionic liquid was prepared by mixing etodolac with lidocaine (1:1, mol/mol). Both the free drug and the transformed ionic liquid were characterized by differential scanning colorimetry (DSC), infrared spectroscopy (IR), and saturation concentration measurements. In addition, in vitro skin-permeation testing was carried out via an ionic liquid-containing patch (Etoreat patch). The lidocaine and etodolac in ionic liquid form led to a relatively lower melting point than either lidocaine or etodolac alone, and this improved the lipophilicity/hydrophilicity of etodolac. In vitro skin-permeation testing demonstrated that the Etoreat patch significantly increased the skin permeation of etodolac (9.3-fold) compared with an etodolac alone patch, although an Etoreat patch did not increase the skin permeation of lidocaine, which was consistent with the results when using a lidocaine alone patch. Lidocaine appeared to self-sacrificially improve the skin permeation of etodolac via its transformation into an ionic liquid. The data suggest that ionic liquids composed of approved drugs may substantially expand the formulation preparation method to meet the challenges of drugs which are characterized by poor rates of transdermal absorption. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

Mesoporous poly(ionic liquid) supported palladium(II) catalyst for oxidative coupling of benzene under atmospheric oxygen

NASA Astrophysics Data System (ADS)

Liu, Yangqing; Wang, Kai; Hou, Wei; Shan, Wanjian; Li, Jing; Zhou, Yu; Wang, Jun

2018-01-01

Multi-functional mesoporous poly(ionic liquid) (MPIL) containing pyridine-based ionic liquid (IL) moieties and adjacent double sbnd COOH groups was synthesized through the free radical copolymerization of IL monomer N-propane sulfonate-4-vinylpyridine, maleic anhydride and divinylbenzene. Palladium(II) species were anchored on this MPIL support, affording the first efficient heterogeneous catalyst for the oxidative coupling of benzene to biphenyl under atmospheric oxygen at low temperature. The biphenyl yield of 15.0% (selectivity: 98.5%, turnover number: 62) was even higher than the one over the homogeneous counterpart palladium acetate. The catalyst can be facilely separated and reused. The IL moiety in the polymeric framework endowed the formation of immobilized palladium(II) species with high electrophilicity, which responds to the high performance.

Ionic Liquids and New Proton Exchange Membranes for Fuel Cells

NASA Technical Reports Server (NTRS)

Belieres, Jean-Philippe

2004-01-01

There is currently a great surge of activity in fuel cell research as laboratories across the world seek to take advantage of the high energy capacity provided by &el cells relative to those of other portable electrochemical power systems. Much of this activity is aimed at high temperature fie1 cells, and a vital component of such &el cells must be the availability of a high temperature stable proton-permeable membrane. NASA Glenn Research Center is greatly involved in developing this technology. Other approaches to the high temperature fuel cell involve the use of single- component or almost-single-component electrolytes that provide a path for protons through the cell. A heavily researched case is the phosphoric acid fuel cell, in which the electrolyte is almost pure phosphoric acid and the cathode reaction produces water directly. The phosphoric acid fie1 cell delivers an open circuit voltage of 0.9 V falling to about 0.7 V under operating conditions at 170 C. The proton transport mechanism is mainly vehicular in character according to the viscosity/conductance relation. Here we describe some Proton Transfer Ionic Liquids (PTILs) with low vapor pressure and high temperature stability that have conductivities of unprecedented magnitude for non-aqueous systems. The first requirement of an ionic liquid is that, contrary to experience with most liquids consisting of ions, it must have a melting point that is not much above room temperature. The limit commonly suggested is 100 C. PTILs constitute an interesting class of non-corrosive proton-exchange electrolyte, which can serve well in high temperature (T = 100 - 250 C) fuel cell applications. We will present cell performance data showing that the open circuit voltage output, and the performance of a simple H2(g)Pt/PTIL/Pt/O2(g) fuel cell may be superior to those of the equivalent phosphoric acid electrolyte fuel cell both at ambient temperature and temperatures up to and above 200 C. My work at NASA Glenn Research Center during this summer is to develop and characterize proton exchange membranes doped with ionic liquids. The main techniques used to characterize these materials are: Impedance Spectroscopy, NMR, DSC, TGA, DMA, IR, and SEM ...

FY04 LDRD Final Report: Interaction of Viruses with Membranes and Soil Materials

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

Schaldach, C M

2005-02-08

The influence of ionic strength on the electrostatic interaction of viruses with environmentally relevant surfaces was determined for three viruses, MS2, Q{beta} and Norwalk. The environmental surface is modeled as charged Gouy-Chapman plane with and without a finite atomistic region (patch) of opposite charge. The virus is modeled as a particle comprised of ionizable amino acid residues in a shell surrounding a spherical RNA core of negative charge, these charges being compensated for by a Coulomb screening due to intercalated ions. Surface potential calculations for each of the viruses show excellent agreement with electrophoretic mobility and zeta potential measurements asmore » a function of pH. The results indicate that the electrostatic interaction between the virus and the planar surface, mitigated by the ionic strength of the solute, is dependent upon the spatial distribution of the amino acid residues in the different viruses. Specifically, the order of interaction energies with the patch (MS2 greatest at 5 mM; Norwalk greatest at 20 mM) is dependent upon the ionic strength of the fluid as a direct result of the viral coat amino acid distributions. We have developed an atomistic-scale method of calculation of the binding energy of viruses to surfaces including electrostatic, van der Waals, electron-overlap repulsion, surface charge polarization (images), and hydrophobic effects. The surface is treated as a Gouy-Chapman plane allowing inclusion of pH and ionic strength effects on the electrostatic potential at each amino acid charge. Van der Waals parameters are obtained from the DREIDING force field and from Hamaker constant measurements. We applied this method to the calculation of the Cowpea Mosaic Virus (CPMV), a negatively charged virus at a pH of 7.0, and find that the viral-gold surface interaction is very long range for both signs of surface potential, a result due to the electrostatic forces. For a negative (Au) surface potential of -0.05 volts, a nearly 4 eV barrier must be overcome to reach 1 nm from the surface.« less

On the chemical stabilities of ionic liquids.

PubMed

Sowmiah, Subbiah; Srinivasadesikan, Venkatesan; Tseng, Ming-Chung; Chu, Yen-Ho

2009-09-25

Ionic liquids are novel solvents of interest as greener alternatives to conventional organic solvents aimed at facilitating sustainable chemistry. As a consequence of their unusual physical properties, reusability, and eco-friendly nature, ionic liquids have attracted the attention of organic chemists. Numerous reports have revealed that many catalysts and reagents were supported in the ionic liquid phase, resulting in enhanced reactivity and selectivity in various important reaction transformations. However, synthetic chemists cannot ignore the stability data and intermolecular interactions, or even reactions that are directly applicable to organic reactions in ionic liquids. It is becoming evident from the increasing number of reports on use of ionic liquids as solvents, catalysts, and reagents in organic synthesis that they are not totally inert under many reaction conditions. While in some cases, their unexpected reactivity has proven fortuitously advantageous in others is has been a problem, it is imperative that when selecting an ionic liquid for a particular synthetic application, attention be paid to its compatibility with the reaction conditions. Even though, more than 200 room temperature ionic liquids are known, only a few reports have commented their effects on reaction mechanisms or rate/stability. Therefore, rather than attempting to give a comprehensive overview of ionic liquid chemistry, this review focuses on the non-innocent nature of ionic liquids, with a decided emphasis to clearly illuminate the ability of ionic liquids to affect the mechanistic aspects of some organic reactions thereby affecting and promoting the yield and selectivity.

Coagulation removal of humic acid-stabilized carbon nanotubes from water by PACl: influences of hydraulic condition and water chemistry.

PubMed

Ma, Si; Liu, Changli; Yang, Kun; Lin, Daohui

2012-11-15

Discharged carbon nanotubes (CNTs) can adsorb the widely-distributed humic acid (HA) in aquatic environments and thus be stabilized. HA-stabilized CNTs can find their way into and challenge the potable water treatment system. This study investigated the efficiency of coagulation and sedimentation techniques in the removal of the HA-stabilized multi-walled carbon nanotubes (MWCNTs) using polyaluminum chloride (PACl) as a coagulant, with a focus on the effects of hydraulic conditions and water chemistry. Stirring speeds in the mixing and reacting stages were gradually changed to examine the effect of the hydraulic conditions on the removal rate. The stirring speed in the reacting stage affected floc formation and thereby had a greater impact on the removal rate than the stirring speed in the mixing stage. Water chemistry factors such as pH and ionic strength had a significant effect on the stability of MWCNT suspension and the removal efficiency. Low pH (4-7) was favorable for saving the coagulant and maintaining high removal efficiency. High ionic strength facilitated the destabilization of the HA-stabilized MWCNTs and thereby lowered the required PACl dosage for the coagulation. However, excessively high ionic strength (higher than the critical coagulation concentration) decreased the maximum removal rate, probably by inhibiting ionic activity of PACl hydrolyzate in water. These results are expected to shed light on the potential improvement of coagulation removal of aqueous stabilized MWCNTs in water treatment systems. Copyright © 2012 Elsevier B.V. All rights reserved.

Low severity coal conversion by ionic hydrogenation: Quarterly report, October--December 1988

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

Maioriello, J.; Larsen, J.W.

1988-12-31

A newly developed reaction system consisting of H/sub 2/O:BF/sub 3//H/sub 2//(CH/sub 3/CN)/sub 2/PtCl/sub 2/ was applied to the ionic hydrogenation of aromatic and functionalized aromatic compounds. Hydrogenations were carried out in this aqueous system at 50/degree/C and 500 psi H/sub 2/. Aryl ethers were hydrogenated and cleaved, yielding deoxygenated, fully saturated compounds as the major products. Reactions of nitrogen-containing aromatic compounds resulted in partial saturation of aromatic rings without cleavage of the C-N bonds. Aromatic and PNA compounds can be fully or partially hydrogenated depending on their structures. Aromatic thiols, sulfides and thiophenes poison the catalyst; the oxidized sulfur formsmore » (sulfonic acids, sulfones) were not reduced and did not poison the catalyst. It was found that certain aromatic compounds were easier to hydrogenate than others. Ionic hydrogenation of Wyodak cola using a H/sub 2/O:BF/sub 3//H/sub 2//(MeCN)/sub 2/PtCl/sub 2/ resulted in no significant increase in THF extractability (5.8--9.6% THF-extractables, wt) over that of the parent coal (4.6--6.7% THF-extractables, wt). Ionic hydrogenation of a demineralized Wyodak coal (1 M aq. citric acid, reflux 1 day) resulted in a slight increase in THF extractability (10.4%) over the untreated parent coal (5.6--5.8%). 4 refs., 1 fig., 1 tab.« less

Ultrafast fluorescence upconversion technique and its applications to proteins.

PubMed

Chosrowjan, Haik; Taniguchi, Seiji; Tanaka, Fumio

2015-08-01

The basic principles and main characteristics of the ultrafast time-resolved fluorescence upconversion technique (conventional and space-resolved), including requirements for nonlinear crystals, mixing spectral bandwidth, acceptance angle, etc., are presented. Applications to flavoproteins [wild-type (WT) FMN-binding protein and its W32Y, W32A, E13R, E13K, E13Q and E13T mutants] and photoresponsive proteins [WT photoactive yellow protein and its R52Q mutant in solution and as single crystals] are demonstrated. For flavoproteins, investigations elucidating the effects of ionic charges on ultrafast electron transfer (ET) dynamics are summarized. It is shown that replacement of the ionic amino acid Glu13 and the resulting modification of the electrostatic charge distribution in the protein chromphore-binding pocket substantially alters the ultrafast fluorescence quenching dynamics and ET rate in FMN-binding protein. It is concluded that, together with donor-acceptor distances, electrostatic interactions between ionic photoproducts and other ionic groups in the proteins are important factors influencing the ET rates. In WT photoactive yellow protein and the R52Q mutant, ultrafast photoisomerization dynamics of the chromophore (deprotonated trans-p-coumaric acid) in liquid and crystal phases are investigated. It is shown that the primary dynamics in solution and single-crystal phases are quite similar; hence, the photocycle dynamics and structural differences observed at longer time scales arise mostly from the structural restraints imposed by the crystal lattice rigidity versus the flexibility in solution. © 2014 FEBS.

Monitoring the ionic content of exhaled breath condensate in various respiratory diseases by capillary electrophoresis with contactless conductivity detection.

PubMed

Greguš, Michal; Foret, František; Kindlová, Dagmar; Pokojová, Eva; Plutinský, Marek; Doubková, Martina; Merta, Zdeněk; Binková, Ilona; Skřičková, Jana; Kubáň, Petr

2015-05-06

The analysis of an ionic profile of exhaled breath condensate (EBC) by capillary electrophoresis with contactless conductivity detection and double opposite end injection, is demonstrated. A miniature sampler made from a 2 ml syringe and an aluminium cooling cylinder was used for the fast collection of EBC (under one minute). Analysis of the collected EBC was performed in a 60 mM 2-(N-morpholino)ethanesulfonic acid, 60 mM L-histidine background electrolyte with 30 µM cetyltrimethylammonium bromide and 2 mM 18-crown-6 at pH 6, and excellent repeatability of migration times (RSD  <1.3% (n = 7)) and peak areas (RSD  <  7% (n = 7)) of 14 ions (inorganic anions, cations and organic acids) was obtained. It is demonstrated that the analysis of EBC samples obtained from patients with various respiratory diseases (chronic obstructive pulmonary disease, asthma, pulmonary fibrosis, sarcoidosis, cystic fibrosis) is possible in less than five minutes and the ionic profile can be compared with the group of healthy individuals. The analysis of the ionic profile of EBC samples provides a set of data in which statistically significant differences among the groups of patients could be observed for several clinically relevant anions (nitrite, nitrate, acetate, lactate). The developed collection system and method provides a highly reproducible and fast way of collecting and analyzing EBC, with future applicability in point-of-care diagnostics.

Characterization of the interaction between furosemide and bovine serum albumin

NASA Astrophysics Data System (ADS)

Zhou, Neng; Liang, Yi-Zeng; Wang, Ping

2008-01-01

The interaction of furosemide (FU), one kind of potent diuretic, with bovine serum albumin (BSA) has been investigated at physiological acidity (pH 7.40) by fluorescent technique. Displacement experiment with site markers and Synchronous fluorescence clearly reveal that there are non-specific binding sites of FU with BSA. This conclusion was supported by the binding studies in the presence of the hydrophobic probe 1-anilinonaphthalene-8-sulfonic acid (ANS) and in different ionic strength. The binding sites number n and binding constant K were measured. The thermodynamic parameters Δ H°, Δ G°, Δ S° at different temperatures were calculated. The effects of other four diuretics, some common metal ions and bioactive components from herbal medicine on the binding are also considered. The results show only bumetanide has strong effect on FU's binding. Moreover, several data processing methods presently used were evaluated with Data of the same set. Quite different results were obtained from these methods suggesting more attention should be paid to the data processing methods.

Hydrolysis of Hemicellulose and Derivatives-A Review of Recent Advances in the Production of Furfural.

PubMed

Delbecq, Frederic; Wang, Yantao; Muralidhara, Anitha; El Ouardi, Karim; Marlair, Guy; Len, Christophe

2018-01-01

Biobased production of furfural has been known for decades. Nevertheless, bioeconomy and circular economy concepts is much more recent and has motivated a regain of interest of dedicated research to improve production modes and expand potential uses. Accordingly, this review paper aims essentially at outlining recent breakthroughs obtained in the field of furfural production from sugars and polysaccharides feedstocks. The review discusses advances obtained in major production pathways recently explored splitting in the following categories: (i) non-catalytic routes like use of critical solvents or hot water pretreatment, (ii) use of various homogeneous catalysts like mineral or organic acids, metal salts or ionic liquids, (iii) feedstock dehydration making use of various solid acid catalysts; (iv) feedstock dehydration making use of supported catalysts, (v) other heterogeneous catalytic routes. The paper also briefly overviews current understanding of furfural chemical synthesis and its underpinning mechanism as well as safety issues pertaining to the substance. Eventually, some remaining research topics are put in perspective for further optimization of biobased furfural production.

Hydrolysis of hemicellulose and derivatives – A review of recent advances in the production of furfural

NASA Astrophysics Data System (ADS)

Delbecq, Frederic; Wang, Yantao; Muralidhara, Anitha; El Ouardi, Karim; Marlair, Guy; Len, Christophe

2018-05-01

Biobased production of furfural has been known for decades. Nevertheless, bioeconomy and circular economy concepts is much more recent and has motivated a regain of interest of dedicated research to improve production modes and expand potential uses. Accordingly, this review paper aims essentially at outlining recent breakthroughs obtained in the field of furfural production from sugars and polysaccharides feedstocks. The review discusses advances obtained in major production pathways recently explored splitting in the following categories: i) non-catalytic routes like use of critical solvents or hot water pretreatment, ii) use of various homogeneous catalysts like mineral or organic acids, metal salts or ionic liquids, iii) feedstock dehydration making use of various solid acid catalysts; iv) feedstock dehydration making use of supported catalysts, v) other heterogeneous catalytic routes. The paper also briefly overviews current understanding of furfural chemical synthesis and its underpinning mechanism as well as safety issues pertaining to the substance. Eventually, some remaining research topics are put in perspective for further optimization of biobased furfural production.

Supramolecular gels with high strength by tuning of calix[4]arene-derived networks

NASA Astrophysics Data System (ADS)

Lee, Ji Ha; Park, Jaehyeon; Park, Jin-Woo; Ahn, Hyo-Jun; Jaworski, Justyn; Jung, Jong Hwa

2015-03-01

Supramolecular gels comprised of low-molecular-weight gelators are generally regarded as mechanically weak and unable to support formation of free-standing structures, hence, their practical use with applied loads has been limited. Here, we reveal a technique for in situ generation of high tensile strength supramolecular hydrogels derived from low-molecular-weight gelators. By controlling the concentration of hydrochloric acid during hydrazone formation between calix-[4]arene-based gelator precursors, we tune the mechanical and ductile properties of the resulting gel. Organogels formed without hydrochloric acid exhibit impressive tensile strengths, higher than 40 MPa, which is the strongest among self-assembled gels. Hydrogels, prepared by solvent exchange of organogels in water, show 7,000- to 10,000-fold enhanced mechanical properties because of further hydrazone formation. This method of molding also allows the gels to retain shape after processing, and furthermore, we find organogels when prepared as gel electrolytes for lithium battery applications to have good ionic conductivity.

Supramolecular gels with high strength by tuning of calix[4]arene-derived networks

PubMed Central

Lee, Ji Ha; Park, Jaehyeon; Park, Jin-Woo; Ahn, Hyo-Jun; Jaworski, Justyn; Jung, Jong Hwa

2015-01-01

Supramolecular gels comprised of low-molecular-weight gelators are generally regarded as mechanically weak and unable to support formation of free-standing structures, hence, their practical use with applied loads has been limited. Here, we reveal a technique for in situ generation of high tensile strength supramolecular hydrogels derived from low-molecular-weight gelators. By controlling the concentration of hydrochloric acid during hydrazone formation between calix-[4]arene-based gelator precursors, we tune the mechanical and ductile properties of the resulting gel. Organogels formed without hydrochloric acid exhibit impressive tensile strengths, higher than 40 MPa, which is the strongest among self-assembled gels. Hydrogels, prepared by solvent exchange of organogels in water, show 7,000- to 10,000-fold enhanced mechanical properties because of further hydrazone formation. This method of molding also allows the gels to retain shape after processing, and furthermore, we find organogels when prepared as gel electrolytes for lithium battery applications to have good ionic conductivity. PMID:25799459

Specialist gelator for ionic liquids.

PubMed

Hanabusa, Kenji; Fukui, Hiroaki; Suzuki, Masahiro; Shirai, Hirofusa

2005-11-08

Cyclo(l-beta-3,7-dimethyloctylasparaginyl-L-phenylalanyl) (1) and cyclo(L-beta-2-ethylhexylasparaginyl-L-phenylalanyl) (2), prepared from L-asparaginyl-L-phenylalanine methyl ester, have been found to be specialist gelators for ionic liquids. They can gel a wide variety of ionic liquids, including imizazolium, pyridinium, pyrazolidinium, piperidinium, morpholinium, and ammonium salts. The mean minimum gel concentrations (MGCs) necessary to make gels at 25 degrees C were determined for ionic liquids. The gel strength increased at a rate nearly proportional to the concentration of added gelator. The strength of the transparent gel of 1-butylpyridinium tetrafluoroborate ([C(4)py]BF(4)), prepared at a concentration of 60 g L(-1) (gelator 1/[C(4)py]BF(4)), was ca. 1500 g cm(-2). FT-IR spectroscopy indicated that a driving force for gelation was intermolecular hydrogen bonding between amides and that the phase transition from gel to liquid upon heating was brought about by the collapse of hydrogen bonding. The gels formed from ionic liquids were very thermally stable; no melting occurs up to 140 degrees C when the gels were prepared at a concentration of 70 g L(-1) (gelator/ionic liquid). The ionic conductivities of the gels were nearly the same as those of pure ionic liquids. The gelator had electrochemical stability and a wide electrochemical window. When the gels were prepared from ionic liquids containing propylene carbonate, the ionic conductivities of the resulting gels increased to levels rather higher than those of pure ionic liquids. The gelators also gelled ionic liquids containing supporting electrolytes.

The Nature of the Interactions in Triethanolammonium-Based Ionic Liquids. A Quantum Chemical Study.

PubMed

Fedorova, Irina V; Safonova, Lyubov P

2018-05-10

Structural features and interionic interactions play a crucial role in determining the overall stability of ionic liquids and their physicochemical properties. Therefore, we performed high-level quantum-chemical study of different cation-anion pairs representing the building units of protic ionic liquids based on triethanolammonium cation and anions of sulfuric, nitric, phosphoric, and phosphorus acids to provide essential insight into these phenomena at the molecular level. It was shown that every structure is stabilized through multiple H bonds between the protons in the N-H and O-H groups of the cation and different oxygen atoms of the anion acid. Using atoms in molecules topological parameters and natural bond orbital analysis, we determined the nature and strength of these interactions. Our calculations suggest that the N-H group of the cation has more proton donor-like character than the O-H group that makes the N-H···O hydrogen bonds stronger. A close relation between the binding energies of these ion pairs and experimental melting points was established: the smaller the absolute value of the binding energy between ions, the lower is the melting point.

Room temperature ionic liquids interacting with bio-molecules: an overview of experimental and computational studies

NASA Astrophysics Data System (ADS)

Benedetto, Antonio; Ballone, Pietro

2016-03-01

We briefly review experimental and computational studies of room temperature ionic liquids (RTILs) interacting with important classes of biomolecules, including phospholipids, peptides and proteins, nucleic acids and carbohydrates. Most of these studies have been driven by the interest for RTILs applications as solvents. Thus, available experimental data cover primarily thermodynamic properties such as the reciprocal solubility of RTILs and bio-molecules, as well as phase boundaries. Less extensive data are also available on transport properties such as diffusion and viscosity of homogeneous binary (RTILs/biomolecules) and ternary (RTIL/biomolecules/water) solutions. Most of the structural information at the atomistic level, of interest especially for biochemical, pharmaceutical and nanotechnology applications, has been made available by molecular dynamics simulations. Major exceptions to this statement are represented by the results from NMR and circular dichroism spectroscopy, by selected neutron and X-ray scattering data, and by recent neutron reflectometry measurements on lipid bilayers on surfaces, hydrated by water-RTIL solutions. A final section of our paper summarizes new developments in the field of RTILs based on amino acids, that combine in themselves the two main aspects of our discussion, i.e. ionic liquids and bio-molecules.

Polypeptide nanogels with hydrophobic moieties in the cross-linked ionic cores: Synthesis, characterization and implications for anticancer drug delivery

PubMed Central

Kim, Jong Oh; Oberoi, Hardeep S.; Desale, Swapnil; Kabanov, Alexander V.; Bronich, Tatiana K.

2014-01-01

Polymer nanogels have gained considerable attention as a potential platform for drug delivery applications. Here we describe the design and synthesis of novel polypeptide-based nanogels with hydrophobic moieties in the cross-linked ionic cores. Diblock copolymer, poly(ethylene glycol)-b-poly(L-glutamic acid), hydrophobically modified with L-phenylalanine methyl ester moieties was used for controlled template synthesis of nanogels with small size (ca. 70 nm in diameter) and narrow particle size distribution. Steady-state and time-resolved fluorescence studies using coumarin C153 indicated the existence of hydrophobic domains in the ionic cores of the nanogels. Stable doxorubicin-loaded nanogels were prepared at high drug capacity (30 w/w%). We show that nanogels are enzymatically-degradable leading to accelerated drug release under simulated lysosomal acidic pH. Furthermore, we demonstrate that the nanogel-based formulation of doxorubicin is well tolerated and exhibit an improved antitumor activity compared to a free doxorubicin in an ovarian tumor xenograft mouse model. Our results signify the point to a potential of these biodegradable nanogels as attractive carriers for delivery of chemotherapeutics. PMID:23998716

Fractionation of poly(methacrylic acid) and poly(vinyl pyridine) in aqueous and organic mobile phases by multidetector thermal field-flow fractionation.

PubMed

Greyling, Guilaume; Pasch, Harald

2017-08-25

Multidetector thermal field-flow fractionation (ThFFF) is shown to be a versatile characterisation platform that can be used to characterise hydrophilic polymers in a variety of organic and aqueous solutions with various ionic strengths. It is demonstrated that ThFFF fractionates isotactic and syndiotactic poly(methacrylic acid) (PMAA) as well as poly(2-vinyl pyridine) (P2VP) and poly(4-vinyl pyridine) (P4VP) according to microstructure in organic solvents and that the ionic strength of the mobile phase has no influence on the retention behaviour of the polymers. With regard to aqueous solutions, it is shown that, despite the weak retention, isotactic and syndiotactic PMAA show different retention behaviours which can qualitatively be attributed to microstructure. Additionally, it is shown that the ionic strength of the mobile phase has a significant influence on the thermal diffusion of polyelectrolytes in aqueous solutions and that the addition of an electrolyte is essential to achieve a microstructure-based separation of P2VP and P4VP in aqueous solutions. Copyright © 2017 Elsevier B.V. All rights reserved.

Solid-state acid-base interactions in complexes of heterocyclic bases with dicarboxylic acids: crystallography, hydrogen bond analysis, and 15N NMR spectroscopy.

PubMed

Li, Z Jane; Abramov, Yuriy; Bordner, Jon; Leonard, Jason; Medek, Ales; Trask, Andrew V

2006-06-28

A cancer candidate, compound 1, is a weak base with two heterocyclic basic nitrogens and five hydrogen-bonding functional groups, and is sparingly soluble in water rendering it unsuitable for pharmaceutical development. The crystalline acid-base pairs of 1, collectively termed solid acid-base complexes, provide significant increases in the solubility and bioavailability compared to the free base, 1. Three dicarboxylic acid-base complexes, sesquisuccinate 2, dimalonate 3, and dimaleate 4, show the most favorable physicochemical profiles and are studied in greater detail. The structural analyses of the three complexes using crystal structure and solid-state NMR reveal that the proton-transfer behavior in these organic acid-base complexes vary successively correlating with Delta pKa. As a result, 2 is a neutral complex, 3 is a mixed ionic and zwitterionic complex and 4 is an ionic salt. The addition of the acidic components leads to maximized hydrogen bond interactions forming extended three-dimensional networks. Although structurally similar, the packing arrangements of the three complexes are considerably different due to the presence of multiple functional groups and the flexible backbone of 1. The findings in this study provide insight into the structural characteristics of complexes involving heterocyclic bases and carboxylic acids, and demonstrate that X-ray crystallography and 15N solid-state NMR are truly complementary in elucidating hydrogen bonding interactions and the degree of proton transfer of these complexes.

Strongly coupled Sm0.2Ce0.8O2-Na2CO3 nanocomposite for low temperature solid oxide fuel cells: One-step synthesis and super interfacial proton conduction

NASA Astrophysics Data System (ADS)

Zhang, Guanghong; Li, Wenjian; Huang, Wen; Cao, Zhiqun; Shao, Kang; Li, Fengjiao; Tang, Chaoyun; Li, Cuihua; He, Chuanxin; Zhang, Qianling; Fan, Liangdong

2018-05-01

Highly conductive ceria-carbonate composite represents one type of most promising electrolyte materials for low temperature solid oxide fuel cells (SOFCs). Composites with large oxide-carbonate interface and homogeneous element/phase distribution are desirable to further enhance electrical properties and to study the ionic conduction mechanism. In this work, we report the successful synthesis of element/phase well-distributed, interfacial strongly coupled Sm0.2Ce0.8O2-Na2CO3 (NSDC) nanocomposite with different residual carbonate contents by an in-situ one-pot one-step citric acid-nitrate combustion method. Interestingly, NSDC shows distinct properties over those prepared by conventional methods and improved ionic conductivity. In particular, NSDC9010 nanocomposite displays a proton conductivity of 0.044 S cm-1 at 650 °C, which is 3-5 times higher than the oxide proton conductors. Electrolyte supported SOFCs based on the resultant nanocomposite electrolyte, NSDC9010, give the best power output of 281.5 mW cm-2 at 600 °C with LiNiO2 symmetric electro-catalysts. The excellent ionic conductivity and fuel cell performance are correlated with the unique core-shell structure, good phase distribution and large interfacial area induced by the one-step fabrication method, the strong coupling between oxide and carbonate as verified by the differential thermal and Raman spectroscopy characterization results and the optimal interfacial carbonate layer thickness by intentionally adjusting of carbonate contents.

Computational analysis of the solvation of coffee ingredients in aqueous ionic liquid mixtures.

PubMed

Zeindlhofer, Veronika; Khlan, Diana; Bica, Katharina; Schröder, Christian

2017-01-13

In this paper, we investigate the solvation of coffee ingredients including caffeine, gallic acid as representative for phenolic compounds and quercetin as representative for flavonoids in aqueous mixtures of the ionic liquid 1-ethyl-3-methylimidazolium acetate [C 2 mim][OAc] at various concentrations. Due to the anisotropy of the solutes we show that classical Kirkwood-Buff theory is not appropriate to study solvation effects with increasing ionic liquid content. However, excess coordination numbers as well as the mean residence time of solvent molecules at the surface of the solutes can be determined by Voronoi tessellation. Since the volume of the hydration shells is also available by this method, solvation free energies will be discussed as a function of the ionic liquid concentration to yield a physical meaningful picture of solvation for the anisotropic solutes. Hydrogen bonding capabilities of the solutes and their relevance for experimental extraction yields from spent coffee grounds are also discussed.

The effect of ionic membrane properties on the performance of ionic polymer-metal composite (IPMC) actuator

NASA Astrophysics Data System (ADS)

Jho, Jae Y.; Han, Man J.; Park, Jong H.; Lee, Jang Y.; Wang, Hyuck S.

2005-05-01

On purpose to overcome the limit of conventional ionic polymer-metal composites (IPMC) using the commercial ionic membranes, novel IPMCs with radiation-grafted ion-exchange membranes were prepared. Poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-co-HFP) and poly(ethylene-co-tetrafluoroethylene) (ETFE) were radiation-grafted with styrene, and then sulfonated. The properties of the membranes were modulated by controlling the amount of polystyrene sulfonic acid (PSSA) groups in the membranes. The amount of PSSA groups were tuned by controlling the total absorbed dose of γ-ray. The membranes were characterized by measuring the water-uptake, the ion-exchange capacity, and the ion conductivity. The performance of the IPMCs using these membranes were analyzed with laser displacement meter. They exhibited much larger bending displacement in comparison with Nafion-based IPMC. With increasing the amount of PSSA groups, the maximum displacement and the bending speed were remarkably increased. The results made sure that the property of ion-exchange membrane was the key element affecting the actuation performance of IPMC.

Oxidized template-synthesized mesoporous carbon with pH-dependent adsorption activity: A promising adsorbent for removal of hydrophilic ionic liquid

NASA Astrophysics Data System (ADS)

Zhang, Ling; Cao, Wugang; Alvarez, Pedro J. J.; Qu, Xiaolei; Fu, Heyun; Zheng, Shourong; Xu, Zhaoyi; Zhu, Dongqiang

2018-05-01

Aiming to remove ionic liquid pollutants from water, an ordered mesoporous carbon CMK-3 (OMC) was prepared and modified by oxidation with nitric acid. A commercial microporous activated carbon adsorbent, Filtrasorb-300 (AC), was used as benchmark. Boehm titration showed that oxidized OMC had a substantially higher oxygen content than oxidized AC. Adsorption of the hydrophilic imidazolium-based ionic liquid 1-Butyl-3-methylimidazolium chloride ([Bmim]Cl) on OMC and AC was well-described by the Freundlich isotherm model. Surface oxidation markedly enhanced [Bmim]Cl adsorption by both OMC and AC. Nevertheless, [Bmim]Cl adsorption was much higher on oxidized OMC than on oxidized AC. Increasing pH had negligible influence on [Bmim]Cl adsorption on pristine OMC, but enhanced adsorption on oxidized OMC. Regeneration tests showed stable performance of oxidized OMC over five adsorption-desorption cycles. Thus, oxidized OMC can be a highly effective adsorbent for the removal of hydrophilic ionic liquids from water.

Structural origins of pH and ionic strength effects on protein stability. Acid denaturation of sperm whale apomyoglobin.

PubMed

Yang, A S; Honig, B

1994-04-15

A recently developed approach to calculate the pH dependence of protein stability from three-dimensional structure information is applied to the analysis of acid denaturation of sperm whale apomyoglobin. The finite difference Poisson-Boltzmann method is used to calculate pKa values and these are used to obtain titration curves for the folded protein as well as for compact intermediates. The total electrostatic free energy change involved in apomyoglobin unfolding is then evaluated. Calculations are carried out of the unfolding free energy of the native (N) and the compact intermediate (I) of apomyoglobin relative to the unfolded state (U) over a range of pH at various ionic strengths. The contributions from key ionizable groups to the unfolding process are discussed. For the acid-induced partial unfolding of apomyoglobin near pH 5, the transition from N to I is found to be driven by three histidines that are exposed when the B, C, D and E helices unfold. Similarly, the unfolding of the compact intermediate I consisting of the A, G and H helices is driven primarily by a few carboxylic acids with low pKa values in the compact state. This picture is in contrast to the view which attributes acid denaturation to electrostatic repulsion resulting from the build up of positive charge. In fact, charge-charge interactions in myoglobin are found to be attractive at all pH values where the protein unfolds. pH-dependent changes in these interactions contribute to acid denaturation but other electrostatic effects, such as hydrogen bonding and solvation, are important as well. The effect of increasing ionic strength on unfolding is attributed to the decrease of attractive charge-charge interactions which destabilize the N state relative to I, but stabilize the I state relative to U by reducing the pKa shifts of a few critical carboxylic acids. The I state is found to be more stable than U at neutral pH thus accounting for its presence as an intermediate on the protein folding pathway. Our results have implications for the origins of compact intermediates or "molten globule" states.

Nanoporous membranes with electrochemically switchable, chemically stabilized ionic selectivity

NASA Astrophysics Data System (ADS)

Small, Leo J.; Wheeler, David R.; Spoerke, Erik D.

2015-10-01

Nanopore size, shape, and surface charge all play important roles in regulating ionic transport through nanoporous membranes. The ability to control these parameters in situ provides a means to create ion transport systems tunable in real time. Here, we present a new strategy to address this challenge, utilizing three unique electrochemically switchable chemistries to manipulate the terminal functional group and control the resulting surface charge throughout ensembles of gold plated nanopores in ion-tracked polycarbonate membranes 3 cm2 in area. We demonstrate the diazonium mediated surface functionalization with (1) nitrophenyl chemistry, (2) quinone chemistry, and (3) previously unreported trimethyl lock chemistry. Unlike other works, these chemistries are chemically stabilized, eliminating the need for a continuously applied gate voltage to maintain a given state and retain ionic selectivity. The effect of surface functionalization and nanopore geometry on selective ion transport through these functionalized membranes is characterized in aqueous solutions of sodium chloride at pH = 5.7. The nitrophenyl surface allows for ionic selectivity to be irreversibly switched in situ from cation-selective to anion-selective upon reduction to an aminophenyl surface. The quinone-terminated surface enables reversible changes between no ionic selectivity and a slight cationic selectivity. Alternatively, the trimethyl lock allows ionic selectivity to be reversibly switched by up to a factor of 8, approaching ideal selectivity, as a carboxylic acid group is electrochemically revealed or hidden. By varying the pore shape from cylindrical to conical, it is demonstrated that a controllable directionality can be imparted to the ionic selectivity. Combining control of nanopore geometry with stable, switchable chemistries facilitates superior control of molecular transport across the membrane, enabling tunable ion transport systems.Nanopore size, shape, and surface charge all play important roles in regulating ionic transport through nanoporous membranes. The ability to control these parameters in situ provides a means to create ion transport systems tunable in real time. Here, we present a new strategy to address this challenge, utilizing three unique electrochemically switchable chemistries to manipulate the terminal functional group and control the resulting surface charge throughout ensembles of gold plated nanopores in ion-tracked polycarbonate membranes 3 cm2 in area. We demonstrate the diazonium mediated surface functionalization with (1) nitrophenyl chemistry, (2) quinone chemistry, and (3) previously unreported trimethyl lock chemistry. Unlike other works, these chemistries are chemically stabilized, eliminating the need for a continuously applied gate voltage to maintain a given state and retain ionic selectivity. The effect of surface functionalization and nanopore geometry on selective ion transport through these functionalized membranes is characterized in aqueous solutions of sodium chloride at pH = 5.7. The nitrophenyl surface allows for ionic selectivity to be irreversibly switched in situ from cation-selective to anion-selective upon reduction to an aminophenyl surface. The quinone-terminated surface enables reversible changes between no ionic selectivity and a slight cationic selectivity. Alternatively, the trimethyl lock allows ionic selectivity to be reversibly switched by up to a factor of 8, approaching ideal selectivity, as a carboxylic acid group is electrochemically revealed or hidden. By varying the pore shape from cylindrical to conical, it is demonstrated that a controllable directionality can be imparted to the ionic selectivity. Combining control of nanopore geometry with stable, switchable chemistries facilitates superior control of molecular transport across the membrane, enabling tunable ion transport systems. Electronic supplementary information (ESI) available: Experimental procedures, synthesis, and characterization of molecules 1, 2 and 3. Explanation of the electrochemical method for approximating nanopore diameter. Additional XPS spectra. See DOI: 10.1039/C5NR02939B

Investigation of Pu(IV)-acetohydroxamic acid complex by solvent extraction with di(2-ethylhexyl) phosphoric acid

NASA Astrophysics Data System (ADS)

Brown, M. Alex; Paulenova, Alena; Tkac, Peter

2010-03-01

The stability constant of the Pu(IV)-acetohydroxamic acid complex Pu(AHA)3+ at 1 M ionic strength (pH = 0) has been investigated by method of solvent extraction. Di(2-ethylhexyl) phosphoric acid (HDEHP) was used to extract Pu(IV) from perchloric and nitric acid media at various AHA concentrations. Distribution ratios over a range of ligand concentrations were used in conjunction with graphical methods to obtain logβ1 = 14.3 ± 0.03 in perchloric acid. The stability constant determined from solutions in nitric acid was excluded because of the uncertainty in plutonium speciation.

Correlating morphology to dc conductivity in polymerized ionic liquids

NASA Astrophysics Data System (ADS)

Iacob, Ciprian; Matusmoto, Atsushi; Inoue, Tadashi; Runt, James

Polymerized ionic liquids (PILs) combine the attractive mechanical characteristics of polymers and unique physico-chemical properties of low molecular weight ionic liquids in the same material. PILs have shown remarkable advantages when employed in electrochemical devices such as dye-sensitized solar cells and lithium batteries, among others. Understanding their ionic transport mechanism is the key for designing highly conductive PILs. In the current study, the correlation between morphology and charge transport in two homologous series of PILs with systematic variation of the alkyl chain length and anions is investigated using broadband dielectric spectroscopy, rheology, differential scanning calorimetry and X-ray scattering. As the alkyl chain length increases, the backbone-to-backbone separation increases, and dc-conductivity consequently decreases. The cations dominate structural dynamics since they are attached to the polymer chains, while the anions are smaller and more mobile ionic species thereby controlling the ionic conductivity. Further interpretation of decoupling of dc conductivity from the segmental relaxation enabled the correlation between polymer morphology and dc conductivity. Supported by the National Science Foundation, Polymers Program.

Wintertime water-soluble aerosol composition and particle water content in Fresno, California

NASA Astrophysics Data System (ADS)

Parworth, Caroline L.; Young, Dominique E.; Kim, Hwajin; Zhang, Xiaolu; Cappa, Christopher D.; Collier, Sonya; Zhang, Qi

2017-03-01

The composition and concentrations of water-soluble gases and ionic aerosol components were measured from January to February 2013 in Fresno, CA, with a particle-into-liquid sampler with ion chromatography and annular denuders. The average (±1σ) ionic aerosol mass concentration was 15.0 (±9.4) µg m-3, and dominated by nitrate (61%), followed by ammonium, sulfate, chloride, potassium, nitrite, and sodium. Aerosol-phase organic acids, including formate and glycolate, and amines including methylaminium, triethanolaminium, ethanolaminium, dimethylaminium, and ethylaminium were also detected. Although the dominant species all came from secondary aerosol formation, there were primary sources of ionic aerosols as well, including biomass burning for potassium and glycolate, sea spray for sodium, chloride, and dimethylamine, and vehicles for formate. Particulate methanesulfonic acid was also detected and mainly associated with terrestrial sources. On average, the molar concentration of ammonia was 49 times greater than nitric acid, indicating that ammonium nitrate formation was limited by nitric acid availability. Particle water was calculated based on the Extended Aerosol Inorganics Model (E-AIM) thermodynamic prediction of inorganic particle water and κ-Köhler theory approximation of organic particle water. The average (±1σ) particle water concentration was 19.2 (±18.6) µg m-3, of which 90% was attributed to inorganic species. The fractional contribution of particle water to total fine particle mass averaged at 36% during this study and was greatest during early morning and night and least during the day. Based on aqueous-phase concentrations of ions calculated by using E-AIM, the average (±1σ) pH of particles in Fresno during the winter was estimated to be 4.2 (±0.2).

Ionic Liquid Confined in Mesoporous Polymer Membrane with Improved Stability for CO2/N2 Separation

PubMed Central

Tan, Ming; Lu, Jingting; Zhang, Yang; Jiang, Heqing

2017-01-01

Supported ionic liquid membranes (SILMs) have a promising prospect of application in flue gas separation, owing to its high permeability and selectivity of CO2. However, existing SILMs have the disadvantage of poor stability due to the loss of ionic liquid from the large pores of the macroporous support. In this study, a novel SILM with high stability was developed by confining ionic liquid in a mesoporous polymer membrane. First, a mesoporous polymer membrane derived from a soluble, low-molecular-weight phenolic resin precursor was deposited on a porous Al2O3 support, and then 1-ethyl-3-methylimidazolium tetrafluoroborate ([emim][BF4]) was immobilized inside mesopores of phenolic resin, forming the SILM under vacuum. Effects of trans-membrane pressure difference on the SILM separation performance were investigated by measuring the permeances of CO2 and N2. The SILM exhibits a high ideal CO2/N2 selectivity of 40, and an actual selectivity of approximately 25 in a mixed gas (50% CO2 and 50% N2) at a trans-membrane pressure difference of 2.5 bar. Compared to [emim][BF4] supported by polyethersulfone membrane with a pore size of around 0.45 μm, the [emim][BF4] confined in a mesoporous polymer membrane exhibits an improved stability, and its separation performance remained stable for 40 h under a trans-membrane pressure difference of 1.5 bar in a mixed gas before the measurement was intentionally stopped. PMID:28961187

Hydrogen-bonding interactions and protic equilibria in room-temperature ionic liquids containing crown ethers.

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

Marin, T.; Shkrob, I.; Dietz, M.

2011-04-14

Nuclear magnetic resonance (NMR) spectroscopy has been used to study hydrogen-bonding interactions between water, associated and dissociated acids (i.e., nitric and methanesulfonic acids), and the constituent ions of several water-immiscible room-temperature ionic liquids (ILs). In chloroform solutions also containing a crown ether (CE), water molecules strongly associate with the IL ions, and there is rapid proton exchange between these bound water molecules and hydronium associated with the CE. In neat ILs, the acids form clusters differing in their degree of association and ionization, and their interactions with the CEs are weak. The CE can either promote proton exchange between differentmore » clusters in IL solution when their association is weak or inhibit such exchange when the association is strong. Even strongly hydrophobic ILs are shown to readily extract nitric acid from aqueous solution, typically via the formation of a 1:1:1 {l_brace}H{sub 3}O{sup +} {center_dot} CE{r_brace}NO{sub 3}{sup -} complex. In contrast, the extraction of methanesulfonic acid is less extensive and proceeds mainly by IL cation-hydronium ion exchange. The relationship of these protic equilibria to the practical application of hydrophobic ILs (e.g., in spent nuclear fuel reprocessing) is discussed.« less

Chemical dynamics of acidity and heavy metals in a mine water-polluted soil during decontamination using clean water.

PubMed

Chen, A; Lin, C; Lu, W; Ma, Y; Bai, Y; Chen, H; Li, J

2010-03-15

A column leaching experiment was conducted to investigate the chemical dynamics of the percolating water and washed soil during decontamination of an acidic mine water-polluted soil. The results show that leaching of the contaminated soil with clean water rapidly reduced soluble acidity and ion concentrations in the soils. However, only <20% of the total actual acidity in the soil column was eliminated after 30 leaching cycles. It is likely that the stored acidity continues to be released to the percolating water over a long period of time. During the column leaching, dissolved Cu and Pb were rapidly leached out, followed by mobilization of colloidal Cu and Pb from the exchangeable and the oxide-bound fractions as a result of reduced ionic strength in the soil solution. The soluble Fe contained in the soil was rare, probably because the soil pH was not sufficiently low; marked mobility of colloidal Fe took place after the ionic strength of the percolating water was weakened and the mobilized Fe was mainly derived from iron oxides. In contrast with Cu, Pb and Fe, the concentration of leachate Zn and Mn showed a continuously decreasing trend during the entire period of the experiment. (c) 2009 Elsevier B.V. All rights reserved.

Structure, stability and behaviour of nucleic acids in ionic liquids

PubMed Central

Tateishi-Karimata, Hisae; Sugimoto, Naoki

2014-01-01

Nucleic acids have become a powerful tool in nanotechnology because of their conformational polymorphism. However, lack of a medium in which nucleic acid structures exhibit long-term stability has been a bottleneck. Ionic liquids (ILs) are potential solvents in the nanotechnology field. Hydrated ILs, such as choline dihydrogen phosphate (choline dhp) and deep eutectic solvent (DES) prepared from choline chloride and urea, are ‘green’ solvents that ensure long-term stability of biomolecules. An understanding of the behaviour of nucleic acids in hydrated ILs is necessary for developing DNA materials. We here review current knowledge about the structures and stabilities of nucleic acids in choline dhp and DES. Interestingly, in choline dhp, A–T base pairs are more stable than G–C base pairs, the reverse of the situation in buffered NaCl solution. Moreover, DNA triplex formation is markedly stabilized in hydrated ILs compared with aqueous solution. In choline dhp, the stability of Hoogsteen base pairs is comparable to that of Watson–Crick base pairs. Moreover, the parallel form of the G-quadruplex is stabilized in DES compared with aqueous solution. The behaviours of various DNA molecules in ILs detailed here should be useful for designing oligonucleotides for the development of nanomaterials and nanodevices. PMID:25013178

Ion conduction mechanisms and thermal properties of hydrated and anhydrous phosphoric acids studied with 1H, 2H, and 31P NMR.

PubMed

Aihara, Yuichi; Sonai, Atsuo; Hattori, Mineyuki; Hayamizu, Kikuko

2006-12-14

To understand the behaviors of phosphoric acids in fuel cells, the ion conduction mechanisms of phosphoric acids in condensed states without free water and in a monomer state with water were studied by measuring the ionic conductivity (sigma) using AC impedance, thermal properties, and self-diffusion coefficients (D) and spin-lattice relaxation times (T1) with multinuclear NMR. The self-diffusion coefficient of the protons (H+ or H3O+), H2O, and H located around the phosphate were always larger than the diffusion coefficients of the phosphates and the disparity increased with increasing phosphate concentration. The diffusion coefficients of the samples containing D2O paralleled those in the protonated samples. Since the 1H NMR T1 values exhibited a minimum with temperature, it was possible to determine the correlation times and they were found to be of nanosecond order for a distance of nanometer order for a flip. The agreement of the ionic conductivities measured directly and those calculated from the diffusion coefficients indicates that the ion conduction obeys the Nernst-Einstein equation in the condensed phosphoric acids. The proton diffusion plays a dominant role in the ion conduction, especially in the condensed phosphoric acids.

Furfural production from Eucalyptus wood using an Acidic Ionic Liquid.

PubMed

Peleteiro, Susana; Santos, Valentín; Garrote, Gil; Parajó, Juan Carlos

2016-08-01

Eucalyptus globulus wood samples were treated with hot, compressed water to separate hemicelluloses (as soluble saccharides) from a solid phase mainly made up of cellulose and lignin. The liquid phase was dehydrated, and the resulting solids (containing pentoses as well as poly- and oligo- saccharides made up of pentoses) were dissolved and reacted in media containing an Acidic Ionic Liquid (1-butyl-3-methylimidazolium hydrogen sulfate) and a co-solvent (dioxane). The effects of the reaction time on the product distribution were studied at temperatures in the range 120-170°C for reaction times up to 8h, and operational conditions leading to 59.1% conversion of the potential substrates (including pentoses and pentose structural units in oligo- and poly- saccharides) into furfural were identified. Copyright © 2016 Elsevier Ltd. All rights reserved.

Analyzing DNA curvature and its impact on the ionic environment: application to molecular dynamics simulations of minicircles

PubMed Central

Pasi, Marco; Zakrzewska, Krystyna; Maddocks, John H.

2017-01-01

Abstract We propose a method for analyzing the magnitude and direction of curvature within nucleic acids, based on the curvilinear helical axis calculated by Curves+. The method is applied to analyzing curvature within minicircles constructed with varying degrees of over- or under-twisting. Using the molecular dynamics trajectories of three different minicircles, we are able to quantify how curvature varies locally both in space and in time. We also analyze how curvature influences the local environment of the minicircles, notably via increased heterogeneity in the ionic distributions surrounding the double helix. The approach we propose has been integrated into Curves+ and the utilities Canal (time trajectory analysis) and Canion (environmental analysis) and can be used to study a wide variety of static and dynamic structural data on nucleic acids. PMID:28180333

Macromolecular and solution properties of Cepacian: the exopolysaccharide produced by a strain of Burkholderia cepacia isolated from a cystic fibrosis patient.

PubMed

Sist, Paola; Cescutti, Paola; Skerlavaj, Silvia; Urbani, Ranieri; Leitão, Jorge H; Sá-Correia, Isabel; Rizzo, Roberto

2003-09-01

Light scattering and viscosity measurements were carried out on the previously chemically characterised exopolysaccharide produced by a strain of Burkholderia cepacia isolated from a cystic fibrosis patient. The same exopolysaccharide was also produced by other clinical strains in different laboratories. Therefore, the name Cepacian is now proposed for this exopolysaccharide. Experiments performed as a function of the ionic strength on the native polymer revealed a change in the overall shape of the polymer at low ionic strength. This behaviour was absent in the de-acetylated sample. Potentiometric titrations and light scattering experiments carried out on the acidic form of the native polymer revealed the formation of macromolecular aggregates with a stoichiometry n and 2n stabilised by interactions involving the uronic acid residues.

Proton-conducting membrane based on epoxy resin-poly(vinyl alcohol)-sulfosuccinic acid blend and its nanocomposite with sulfonated multiwall carbon nanotubes for fuel-cell application

NASA Astrophysics Data System (ADS)

Kakati, Nitul; Das, Gautam; Yoon, Young Soo

2016-01-01

A blend of poly(vinyl alcohol) (PVA) with diglycidyl ether of bisphenol-A (DGB) in the presence of sulfosuccinic acid (SSA) was investigated as hydrolytically-stable proton-conducting membrane. The PVA modification was carried out by varying the DGB:SSA ratio (20:20, 10:20, and 5:20). A nanocomposite of the blend (20:20) was prepared with sulfonated multiwall carbon nanotubes (viz., 1, 3 and 5 wt%). The water uptake behavior and the proton conductivity of the prepared membranes were evaluated. The ionic conductivity of the membranes and the water uptake behavior depended on the s-MWCNT and the DGB contents. The ionic conductivity showed an enhancement for the blend and for the nanocomposite membrane as compared to the pristine polymer.

[Biological availability of ophthalmic drugs. 1. Increasing drug permeability in the cornea].

PubMed

Masteiková, R; Chalupová, Z; Savickiene, N

2004-03-01

Most eye diseases are treated by topical administration of ophthalmic preparations. Low ophthalmic bioavailability is due to a number of physiological and physicochemical factors. The main obstacle to the penetration of active ingredients to the eye is the layered character of the cornea. Formulation of ophthalmic preparations enabling easier penetration of this biological barrier thus ranks among the most effective ways of improving bioavailability. Penetrability of the cornea can be increased by the following methods: a) adjustment of the actual acidity in such a way that pH of the preparation makes it possible to produce the optimal portion of non-ionized particles; b) incorporation of absorption enhancers (non-ionic tensides, salts of bile acids, some antimicrobial substances, EDTA, cyclodextrins, etc.) into the composition of the preparation, and c) production of prodrugs or ionic pairs.

The structure investigations of dehydroacetic acid and 1,8-diaminonaphthalene condensation product by NMR, MS, and X-ray measurements

NASA Astrophysics Data System (ADS)

Kołodziej, B.; Morawiak, M.; Kamieński, B.; Schilf, W.

2016-05-01

A new unexpected product of condensation reaction of 1,8-diaminonaphthalene (DAN) and carbonyl compound (here: dehydroacetic acid (dha)) was synthesized. Discussion about the molecular structure of possible products of this reaction was done on the base of NMR studies. The structure of the titled product in both DMSO solution and in the solid state was resolved by analysis of its spectral data (X-ray structure analysis, multinuclear NMR in solution and solid state spectra) and MS measurements. The presented studies provided clear evidence that the titled product exists in diluted DMSO solution as the mixture of two kinetic free ionic species whereas in concentrated DMSO solution as well as in the solid state this system forms associated ionic pairs bonded together by hydrogen bonds.

Influence of pH, soil humic/fulvic acid, ionic strength, foreign ions and addition sequences on adsorption of Pb(II) onto GMZ bentonite.

PubMed

Wang, Suowei; Hu, Jun; Li, Jiaxing; Dong, Yunhui

2009-08-15

This work contributed to the adsorption of Pb(II) onto GMZ bentonite in the absence and presence of soil humic acid (HA)/fulvic acid (FA) using a batch technique. The influences of pH from 2 to 12, ionic strengths from 0.004M to 0.05M NaNO(3), soil HA/FA concentrations from 1.6 mg/L to 20mg/L, foreign cations (Li+, Na+, K+), anions (Cl(-), NO(3)(-)), and addition sequences on the adsorption of Pb(II) onto GMZ bentonite were tested. The adsorption isotherms of Pb(II) were determined at pH 3.6+/-0.1 and simulated with the Langmuir, Freundlich, and D-R adsorption models, respectively. The results demonstrated that the adsorption of Pb(II) onto GMZ bentonite increased with increasing pH from 2 to 6. HA was shown to enhance Pb(II) adsorption at low pH, but to reduce Pb(II) adsorption at high pH, whereas FA was shown to decrease Pb(II) adsorption at pH from 2 to 11. The results also demonstrated that the adsorption was strongly dependent on ionic strength and slightly dependent on the concentration of HA/FA. The adsorption of Pb(II) onto GMZ bentonite was dependent on foreign ions in solution. The addition sequences of bentonite/Pb(II)/HA had no effect on the adsorption of Pb(II).

Cu(II) binding by a pH-fractionated fulvic acid

USGS Publications Warehouse

Brown, G.K.; Cabaniss, S.E.; MacCarthy, P.; Leenheer, J.A.

1999-01-01

The relationship between acidity, Cu(II) binding and sorption to XAD resin was examined using Suwannee River fulvic acid (SRFA). The work was based on the hypothesis that fractions of SRFA eluted from an XAD column at various pH's from 1.0 to 12.0 would show systematic variations in acidity and possibly aromaticity which in turn would lead to different Cu(II) binding properties. We measured equilibrium Cu(II) binding to these fractions using Cu2+ ion-selective electrode (ISE) potentiometry at pH 6.0. Several model ligands were also examined, including cyclopentane-1,2,3,4-tetracarboxylic acid (CP-TCA) and tetrahydrofuran-2,3,4,5-tetracarboxylic acid (THF-TCA), the latter binding Cu(II) much more strongly as a consequence of the ether linkage. The SRFA Cu(II) binding properties agreed with previous work at high ionic strength, and binding was enhanced substantially at lower ionic strength, in agreement with Poisson-Boltzmann predictions for small spheres. Determining Cu binding constants (K(i)) by non-linear regression with total ligand concentrations (L(Ti)) taken from previous work, the fractions eluted at varying pH had K(i) similar to the unfractionated SRFA, with a maximum enhancement of 0.50 log units. We conclude that variable-pH elution from XAD does not isolate significantly strong (or weak) Cu(II)-binding components from the SRFA mixture. Copyright (C) 1999 Elsevier Science B.V.

Interaction between common organic acids and trace nucleation species in the Earth's atmosphere.

PubMed

Xu, Yisheng; Nadykto, Alexey B; Yu, Fangqun; Herb, J; Wang, Wei

2010-01-14

Atmospheric aerosols formed via nucleation in the Earth's atmosphere play an important role in the aerosol radiative forcing associated directly with global climate changes and public health. Although it is well-known that atmospheric aerosol particles contain organic species, the chemical nature of and physicochemical processes behind atmospheric nucleation involving organic species remain unclear. In the present work, the interaction of common organic acids with molecular weights of 122, 116, 134, 88, 136, and 150 (benzoic, maleic, malic, pyruvic, phenylacetic, and tartaric acids) with nucleation precursors and charged trace species has been investigated. We found a moderate strong effect of the organic species on the stability of neutral and charged ionic species. In most cases, the free energies of the mixed H(2)SO(4)-organic acid dimer formation are within 1-1.5 kcal mol(-1) of the (H(2)SO(4))(NH(3)) formation energy. The interaction of the organic acids with trace ionic species is quite strong, and the corresponding free energies far exceed those of the (H(3)O(+))(H(2)SO(4)) and (H(3)O(+))(H(2)SO(4))(2) formation. These considerations lead us to conclude that the aforementioned organic acids may possess a substantial capability of stabilizing both neutral and positively charged prenucleation clusters, and thus, they should be studied further with regard to their involvement in the gas-to-particle conversion in the Earth's atmosphere.

Ionic Liquid Fuels for Chemical Propulsion

DTIC Science & Technology

2014-11-20

researchers seeking hypergolic fuels have limited themselves to the extremely toxic and corrosive nitric acid solutions. While important questions remain...storable oxidizer (N204 , nitric acid ) have been synthesized and demonstrated. The bipropellant fuels are based upon salts containing dicyanamide or...20-30% nanoparticle loading but decreases between 10-20%, perhaps indicating an optimal loading concentration for these nanoparticles between 10-20

Distinct Effects of Humic Acid on Transport and Retention of TiO2 Rutile Nanoparticles in Saturated Sand Column

EPA Science Inventory

Distinct effects of humic acid (HA, 0 – 10 mg L-1) on the transport of titanium dioxide (rutile) nanoparticles (nTiO2) through saturated sand columns were observed under conditions of environmental relevance (ionic strength 3 – 200 mM NaCl, pH 5.7 and 9.0). Specifical...

Impact of chelator-induced phytoextraction of cadmium on yield and ionic uptake of maize.

PubMed

Anwar, Sumera; Khan, Shahbaz; Ashraf, M Yasin; Noman, Ali; Zafar, Sara; Liu, Lijun; Ullah, Sana; Fahad, Shah

2017-06-03

Enhanced phytoextraction uses soil chelators to increase the bioavailability of heavy metals. This study tested the effectiveness of ethylenediaminetetraacetic acid (EDTA) and citric acid in enhancing cadmium (Cd) phytoextraction and their effects on the growth, yield, and ionic uptake of maize (Zea mays). Maize seeds of two cultivars were sown in pots treated with 15 (Cd 15 ) or 30 mg Cd kg -1 soil (Cd 30 ). EDTA and citric acid at 0.5 g kg -1 each were applied 2 weeks after germination. Results demonstrated that the growth, yield per plant, and total grain weight were reduced by exposure to Cd. EDTA increased the uptake of Cd in shoots, roots, and grains of both maize varieties. Citric acid did not enhance the uptake of Cd, rather it ameliorated the toxicity of Cd, as shown by increased shoot and root length and biomass. Cadmium toxicity reduced the number of grains, rather than the grain size. The maize cultivar Sahiwal-2002 extracted 1.6% and 3.6% of Cd from soil in both Cd+ EDTA treatments. Hence, our study implies that maize can be used to successfully phytoremediate Cd from soil using EDTA, without reducing plant biomass or yield.

LASER APPLICATIONS AND OTHER TOPICS IN QUANTUM ELECTRONICS: Holographic sensors for diagnostics of solution components

NASA Astrophysics Data System (ADS)

Kraiskii, A. V.; Postnikov, V. A.; Suitanov, T. T.; Khamidulin, A. V.

2010-02-01

The properties of holographic sensors of two types are studied. The sensors are based on a three-dimensional polymer-network matrix of copolymers of acrylamide, acrylic acid (which are sensitive to the medium acidity and bivalent metal ions) and aminophenylboronic acid (sensitive to glucose). It is found that a change in the ionic composition of a solution results in changes in the distance between layers and in the diffraction efficiency of holograms. Variations in the shape of spectral lines, which are attributed to the inhomogeneity of a sensitive layer, and nonmonotonic changes in the emulsion thickness and diffraction efficiency were observed during transient processes. The composition of the components of a hydrogel medium is selected for systems which can be used as a base for glucose sensors with the mean holographic response in the region of physiological glucose concentration in model solutions achieving 40 nm/(mmol L-1). It is shown that the developed holographic sensors can be used for the visual and instrumental determination of the medium acidity, alcohol content, ionic strength, bivalent metal salts and the quality of water, in particular, for drinking.

Determination of the parameters controlling swelling of chemically cross-linked pH-sensitive poly(N-vinylimidazole) hydrogels.

PubMed

Molina, M Jesús; Gómez-Antón, M Rosa; Piérola, Inés F

2007-10-25

The number of variables controlling the behavior of ionic gels is large and very often some of them are unknown. The aim of this work is to interpret quantitatively the swelling behavior of pH sensitive gels, with the minimum number of simplifying assumptions. With this purpose, the equilibrium degree of swelling (S) and protonation (alpha) of chemically cross-linked poly(N-vinylimidazole) (PVI) immersed in aqueous salt solutions were measured as a function of the ionic strength (mu), in the whole range of pH. In acid solutions with pH in the range 0 to 4, imidazole moieties become protonated, and PVI behaves as a polyelectrolyte gel: S decreases upon increasing mu both for NaCl and for CaCl(2), with HCl as protonating acid. In aqueous solutions with larger pH, between 4 and 12, the hydrogel is practically neutral, and S increases as mu rises, showing a salting-in effect. From the quantitative analysis of these results, the following facts emerged. Protonation induces chain stiffness (as measured by the non-Gaussian factor) and worsening of the solvent quality of the aqueous media (as measured by the polymer-solvent interaction parameter). For alpha below 33%, swelling seems to be governed by the excess of mobile counterions inside the gel with respect to the bath, with a minor but still significantly negative contribution of the osmotic swelling pressure due to polymer-solvent mixing. Above 33% protonation, it is necessary to consider Manning counterion condensation to get parameters with physical meaning. The crossover between polyelectrolyte and salting-in effects corresponds to alpha and mu values with the same ionic and mixing contributions to the osmotic swelling pressure. The formation of ionic nonpermanent cross-links, with H(2)SO(4) as the protonating acid, was discarded.

Influence of Ionic Strength on the Deposition of Metal-Phenolic Networks.

PubMed

Guo, Junling; Richardson, Joseph J; Besford, Quinn A; Christofferson, Andrew J; Dai, Yunlu; Ong, Chien W; Tardy, Blaise L; Liang, Kang; Choi, Gwan H; Cui, Jiwei; Yoo, Pil J; Yarovsky, Irene; Caruso, Frank

2017-10-10

Metal-phenolic networks (MPNs) are a versatile class of self-assembled materials that are able to form functional thin films on various substrates with potential applications in areas including drug delivery and catalysis. Different metal ions (e.g., Fe III , Cu II ) and phenols (e.g., tannic acid, gallic acid) have been investigated for MPN film assembly; however, a mechanistic understanding of the thermodynamics governing MPN formation remains largely unexplored. To date, MPNs have been deposited at low ionic strengths (<5 mM), resulting in films with typical thicknesses of ∼10 nm, and it is still unclear how a bulk complexation reaction results in homogeneous thin films when a substrate is present. Herein we explore the influence of ionic strength (0-2 M NaCl) on the conformation of MPN precursors in solution and how this determines the final thickness and morphology of MPN films. Specifically, the film thickness increases from 10 nm in 0 M NaCl to 12 nm in 0.5 M NaCl and 15 nm in 1 M NaCl, after which the films grow rougher rather than thicker. For example, the root-mean-square roughness values of the films are constant below 1 M NaCl at 1.5 nm; in contrast, the roughness is 3 nm at 1 M NaCl and increases to 5 nm at 2 M NaCl. Small-angle X-ray scattering and molecular dynamics simulations allow for comparisons to be made with chelated metals and polyelectrolyte thin films. For example, at a higher ionic strength (2 M NaCl), sodium ions shield the galloyl groups of tannic acid, allowing them to extend away from the Fe III center and interact with other MPN complexes in solution to form thicker and rougher films. As the properties of films determine their final performance and application, the ability to tune both thickness and roughness using salts may allow for new applications of MPNs.

SEPARATION OF PLUTONIUM FROM FISSION PRODUCTS BY A COLLOID REMOVAL PROCESS

DOEpatents

Schubert, J.

1960-05-24

A method is given for separating plutonium from uranium fission products. An acidic aqueous solution containing plutonium and uranium fission products is subjected to a process for separating ionic values from colloidal matter suspended therein while the pH of the solution is maintained between 0 and 4. Certain of the fission products, and in particular, zirconium, niobium, lanthanum, and barium are in a colloidal state within this pH range, while plutonium remains in an ionic form, Dialysis, ultracontrifugation, and ultrafiltration are suitable methods of separating plutonium ions from the colloids.

New Efficient Synthesis of 3,4-Dihydropyrimidin-2(1H)-ones Catalyzed by Benzotriazolium-Based Ionic Liquids under Solvent-Free Conditions.

PubMed

Liu, Zhiqing; Ma, Rong; Cao, Dawei; Liu, Chenjiang

2016-04-07

An efficient synthesis of novel 3,4-dihydropyrimidin-2(1H)-ones (DHPMs) and their derivatives, using Brønsted acidic ionic liquid [C₂O₂BBTA][TFA] as a catalyst, from the condensation of aryl aldehyde, β-ketoester and urea was described. Reactions proceeded smoothly for 40 min under solvent-free conditions and gave the desirable products with good to excellent yields (up to 99%). The catalyst could be easily recycled and reused with similar efficacies for at least six cycles.

Ionically self-assembled monolayers (ISAMs)

NASA Astrophysics Data System (ADS)

Janik, John

2001-04-01

Ionically self-assembled monolayers (ISAMs), fabricated by alternate adsorption of cationic and anionic components, yield exceptionally homogeneous thin films with sub-nanometer control of the thickness and relative special location of the component materials. Using organic electrochromic materials such as polyaniline, we report studies of electrochromic responses in ISAM films. Reversible changes in the absorption spectrum are observed with the application of voltages on the order of 1.0 V. Measurements are made using both liquid electrolytes and in all-solid state devices incorporating solid polyelectrolytes such as poly(2-acylamido 2-methyl propane sulfonic acid) (PAMPS).

Femtosecond dynamics in ionic structures of a heart medicine

NASA Astrophysics Data System (ADS)

Gil, M.; Douhal, A.

2006-12-01

Femtosecond studies of ionic structures of milrinone - a medicine used to help the heart to recuperate its life - in acidic and alkaline water solutions show that the intramolecular charge transfer in the cation and in the anion happen in 550 fs and ˜1.2 ps, respectively. These times are longer than 100 fs, observed in the keto (inotropic) form. The transients also show a 2-3 ps component, assigned to cooling and twisting motion in the produced states. The result might be used for a better understanding of other functional molecules.

Reciprocal links between metabolic and ionic events in islet cells. Their relevance to the rhythmics of insulin release.

PubMed

Malaisse, W J

1998-02-01

The notion of reciprocal links between metabolic and ionic events in islet cells and the rhythmics of insulin release is based on (i) the rhythmic pattern of hormonal release from isolated perfused rat pancreas, which supports the concept of an intrapancreatic pacemaker; (ii) the assumption that this phasic pattern is due to the integration of secretory activity in distinct functional units, e.g. distinct islets; and (iii) the fact that reciprocal coupling between metabolic and ionic events is operative in the secretory sequence.

Highly stable ionic-covalent cross-linked sulfonated poly(ether ether ketone) for direct methanol fuel cells

NASA Astrophysics Data System (ADS)

Lei, Linfeng; Zhu, Xingye; Xu, Jianfeng; Qian, Huidong; Zou, Zhiqing; Yang, Hui

2017-05-01

A novel ionic cross-linked sulfonated poly(ether ether ketone) containing equal content of sulfonic acid and pendant tertiary amine groups (TA-SPEEK) has been initially synthesized for the application in direct methanol fuel cells (DMFCs). By adjusting the ratio of p-xylene dibromide to tertiary amine groups of TA-SPEEK, a series of ionic-covalent cross-linked membranes (C-SPEEK-x) with tunable degree of cross-linking are prepared. Compared with the pristine membrane, the ionic and ionic-covalent cross-linked proton exchange membranes (PEMs) exhibit reduced methanol permeability and improved mechanical properties, dimensional and oxidative stability. The proton conductivity and methanol selectivity of protonated TA-SPEEK and C-SPEEK-x at 25 °C is up to 0.109 S cm-1 and 3.88 × 105 S s cm-3, respectively, which are higher than that of Nafion 115. The DMFC incorporating C-SPEEK-25 exhibits a maximum power density as high as 35.3 mW cm-2 with 4 M MeOH at 25 °C (31.8 mW cm-2 for Nafion 115). Due to the highly oxidative stability of the membrane, no obvious performance degradation of the DMFC is observed after more than 400 h operation, indicating such cost-effective ionic-covalent cross-linked membranes have substantial potential as alternative PEMs for DMFC applications.

Gas-phase acidities of nitrated azoles as determined by the extended kinetic method and computations.

PubMed

Nichols, Charles M; Old, William M; Lineberger, W Carl; Bierbaum, Veronica M

2015-01-15

Making use of the extended kinetic method and the alternative method for data analysis, we have experimentally determined ΔH°acid (kcal/mol) for six mononitrated azole species (2-nitropyrrole = 337.0, 3-nitropyrrole = 335.8, 3-nitropyrazole = 330.5, 4-nitropyrazole = 329.5, 2-nitroimidazole = 327.4, and 4-nitroimidazole = 325.0). We report an absolute uncertainty of ±2.2 kcal/mol that arises from the uncertainties of the reference acids; the relative values are known within 0.4 kcal/mol. Combining these experimental ΔH°acid values with ΔS°acid values calculated at the B3LYP/aug-cc-pVTZ level of theory, we report ΔG°acid (kcal/mol) for the nitroazoles (2-nitropyrrole = 329.4, 3-nitropyrrole = 328.4, 3-nitropyrazole = 323.1, 4-nitropyrazole = 322.0, 2-nitroimidazole = 319.7, and 4-nitroimidazole = 317.6); the absolute uncertainties are ±2.4 kcal/mol. In addition to the experimental studies, we have computationally investigated the gas-phase acidities and electron affinities of the azoles in this work, as well as higher-order aza- and dinitro-substituted azoles. We discuss trends in the stabilities of the deprotonated azoles based on aza substitution and nitro group placement. 4-Nitroimidazole has already found use as the anionic component in ionic liquids, and we propose that the additional nitrated azolate ions are potential candidates for the anionic component of ionic liquids.

Selectivity of substrate binding and ionization of 2-methyl-3-hydroxypyridine-5-carboxylic acid oxygenase.

PubMed

Luanloet, Thikumporn; Sucharitakul, Jeerus; Chaiyen, Pimchai

2015-08-01

2-Methyl-3-hydroxypyridine-5-carboxylic acid (MHPC) oxygenase (EC 1.14.12.4) from Pseudomonas sp. MA-1 is a flavin-dependent monooxygenase that catalyzes a hydroxylation and aromatic ring cleavage reaction. The functional roles of two residues, Tyr223 and Tyr82, located ~ 5 Å away from MHPC, were characterized using site-directed mutagenesis, along with ligand binding, product analysis and transient kinetic experiments. Mutation of Tyr223 resulted in enzyme variants that were impaired in their hydroxylation activity and had Kd values for substrate binding 5-10-fold greater than the wild-type enzyme. Because this residue is adjacent to the water molecule that is located next to the 3-hydroxy group of MHPC, the results indicate that the interaction between Tyr223, H2 O and the 3-hydroxyl group of MHPC are important for substrate binding and hydroxylation. By contrast, the Kd for substrate binding of Tyr82His and Tyr82Phe variants were similar to that of the wild-type enzyme. However, only ~ 40-50% of the substrate was hydroxylated in the reactions of both variants, whereas most of the substrate was hydroxylated in the wild-type enzyme reaction. In free solution, MHPC or 5-hydroxynicotinic acid exists in a mixture of monoanionic and tripolar ionic forms, whereas only the tripolar ionic form binds to the wild-type enzyme. The binding of tripolar ionic MHPC would allow efficient hydroxylation through an electrophilic aromatic substitution mechanism. For the Tyr82His and Tyr82Phe variants, both forms of substrates can bind to the enzymes, indicating that the mutation at Tyr82 abolished the selectivity of the enzyme towards the tripolar ionic form. Transient kinetic studies indicated that the hydroxylation rate constants of both Tyr82 variants are approximately two- to 2.5-fold higher than that of the wild-type enzyme. Altogether, our findings suggest that Tyr82 is important for the binding selectivity of MHPC oxygenase towards the tripolar ionic species, whereas the interaction between Tyr223 and the substrate is important for ensuring hydroxylation. These results highlight how the active site of a flavoenzyme is able to deal with the presence of multiple forms of a substrate in solution and ensure efficient hydroxylation. © 2015 FEBS.

Characterization of a supported ionic liquid membrane used for the removal of cyanide from wastewater.

PubMed

Xue, Juan Qin; Liu, Ni Na; Li, Guo Ping; Dang, Long Tao

2017-12-01

This work evaluated the performance of ionic liquids (ILs) in supported liquid membranes in the removal of total cyanide from wastewater. Membranes were characterized by scanning electron microscopy and contact angle measurements to study the membrane morphology and wetting ability. In particular, the effects of operational parameters such as membrane immersion time, feed-phase concentration, and pH on cyanide removal were investigated. ILs are organic salts that are entirely composed of organic cations and either organic or inorganic anions. Since their vapor pressure is negligible, they can be handled easily; this characteristic gives rise to their 'green' nature. In this study, a hydrophobic IL, 1-butyl-3-methylimidazolium hexafluorophosphate ([Bmim]PF 6 ), was immobilized in the pores of a solid polymeric support made of polyvinylidene fluoride. The optimal conditions were as follows: 1 hour membrane immersion time, 312.24 mg/L feed-phase concentration, a feed-phase pH of 4, 3% NaOH solution, and 1 hour stirring time. The cyanide removal was 95.31%. The treatment of cyanide using supported ionic liquid membrane (SILM) technology is a method with potential applications in industry.

Solvent-free direct reductive amination by catalytic use of an organotin reagent incorporated on an ionic liquid.

PubMed

Pham, Phuoc Dien; Bertus, Philippe; Legoupy, Stéphanie

2009-11-07

An organotin reagent supported on an ionic liquid was used as a highly effective catalyst (down to 0.1 mol%) for the direct reductive amination of aldehydes and ketones using PhSiH3; this solvent-free method facilitates purification of the products, thus minimizing the contamination by tin.

Surface charge fine tuning of reversed-phase/weak anion-exchange type mixed-mode stationary phases for milder elution conditions.

PubMed

Zimmermann, Aleksandra; Horak, Jeannie; Sánchez-Muñoz, Orlando L; Lämmerhofer, Michael

2015-08-28

A series of new mixed-mode reversed-phase/weak anion-exchange (RP/WAX) phases have been synthesized by immobilization of N-undecenyl-3-α-aminotropane onto thiol-modified silica gel by thiol-ene click chemistry and subsequent introduction of acidic thiol-endcapping functionalities of different type and surface densities. Click chemistry allowed to adjust a controlled surface concentration of the RP/WAX ligand in such a way that a sufficient quantity of residual thiols remained unmodified which have been capped by thiol click with either 3-butenoic acid or allylsulfonic acid as co-ligands. In another embodiment, performic acid oxidation of N-undecenyl-3-α-aminotropane-derivatized thiol-modified silica gave a RP/WAX phase with high density of sulfonic acid end-capping groups. ζ-Potential determinations confirmed the fine-tuned pI of these mixed-mode stationary phases which was shifted from 9.5 to 8.2, 7.8, and 6.5 with 3-butenoic acid and allylsulfonic acid end-capping as well as performic acid oxidation. For acidic solutes, the co-ionic endcapping leads to strongly reduced retention times and clearly allowed elution of these analytes under lower ionic strength thus milder elution conditions. In spite of the acidic endcapping, the new mixed-mode phases maintained their hydrophobic and anion-exchange selectivity as well as their multimodal nature featuring RP and HILIC elution domains at acetonitrile percentages below and above 50%, respectively. Column classification by principal component analysis of an extended retention map in comparison to a set of polar commercial and in-house synthesized stationary phases confirmed complementarity of the new mixed-mode phases with respect to HILIC, polar RP, amino and commercial mixed-mode phases. Copyright © 2015 Elsevier B.V. All rights reserved.

Electrolyte diodes with weak acids and bases. I. Theory and an approximate analytical solution.

PubMed

Iván, Kristóf; Simon, Péter L; Wittmann, Mária; Noszticzius, Zoltán

2005-10-22

Until now acid-base diodes and transistors applied strong mineral acids and bases exclusively. In this work properties of electrolyte diodes with weak electrolytes are studied and compared with those of diodes with strong ones to show the advantages of weak acids and bases in these applications. The theoretical model is a one dimensional piece of gel containing fixed ionizable groups and connecting reservoirs of an acid and a base. The electric current flowing through the gel is measured as a function of the applied voltage. The steady-state current-voltage characteristic (CVC) of such a gel looks like that of a diode under these conditions. Results of our theoretical, numerical, and experimental investigations are reported in two parts. In this first, theoretical part governing equations necessary to calculate the steady-state CVC of a reverse-biased electrolyte diode are presented together with an approximate analytical solution of this reaction-diffusion-ionic migration problem. The applied approximations are quasielectroneutrality and quasiequilibrium. It is shown that the gel can be divided into an alkaline and an acidic zone separated by a middle weakly acidic region. As a further approximation it is assumed that the ionization of the fixed acidic groups is complete in the alkaline zone and that it is completely suppressed in the acidic one. The general solution given here describes the CVC and the potential and ionic concentration profiles of diodes applying either strong or weak electrolytes. It is proven that previous formulas valid for a strong acid-strong base diode can be regarded as a special case of the more general formulas presented here.

High ionic strength narrows the population of sites participating in protein ion-exchange adsorption: A single-molecule study

PubMed Central

Kisley, Lydia; Chen, Jixin; Mansur, Andrea P.; Dominguez-Medina, Sergio; Kulla, Eliona; Kang, Marci; Shuang, Bo; Kourentzi, Katerina; Poongavanam, Mohan-Vivekanandan; Dhamane, Sagar; Willson, Richard C.; Landes, Christy F.

2014-01-01

The retention and elution of proteins in ion-exchange chromatography is routinely controlled by adjusting the mobile phase salt concentration. It has repeatedly been observed, as judged from adsorption isotherms, that the apparent heterogeneity of adsorption is lower at more-eluting, higher ionic strength. Here, we present an investigation into the mechanism of this phenomenon using a single-molecule, super-resolution imaging technique called motion-blur Points Accumulation for Imaging in Nanoscale Topography (mbPAINT). We observed that the number of functional adsorption sites was smaller at high ionic strength and that these sites had reduced desorption kinetic heterogeneity, and thus narrower predicted elution profiles, for the anion-exchange adsorption of α-lactalbumin on an agarose-supported, clustered-charge ligand stationary phase. Explanations for the narrowing of the functional population such as inter-protein interactions and protein or support structural changes were investigated through kinetic analysis, circular dichroism spectroscopy, and microscopy of agarose microbeads, respectively. The results suggest the reduction of heterogeneity is due to both electrostatic screening between the protein and ligand and tuning the steric availability within the agarose support. Overall, we have shown that single molecule spectroscopy can aid in understanding the influence of ionic strength on the population of functional adsorbent sites participating in the ion-exchange chromatographic separation of proteins. PMID:24751557

Multiple functional ionic liquids based dispersive liquid-liquid microextraction combined with high performance chromatography for the determination of phenolic compounds in water samples.

PubMed

Sun, Jian-Nan; Chen, Juan; Shi, Yan-Ping

2014-07-01

A new mode of ionic liquid based dispersive liquid-liquid microextraction (IL-DLLME) is developed. In this work, [C6MIm][PF6] was chosen as the extraction solvent, and two kinds of hydrophilic ionic liquids, [EMIm][BF4] and [BSO3HMIm][OTf], functioned as the dispersive solvent. So in the whole extraction procedure, no organic solvent was used. With the aid of SO3H group, the acidic compound was extracted from the sample solution without pH adjustment. Two phenolic compounds, namely, 2-naphthol and 4-nitrophenol were chosen as the target analytes. Important parameters affecting the extraction efficiency, such as the type of hydrophilic ionic liquids, the volume ratio of [EMIm][BF4] to [BSO3HMIm][OTf], type and volume of extraction solvent, pH value of sample solution, sonication time, extraction time and centrifugation time were investigated and optimized. Under the optimized extraction conditions, the method exhibited good sensitivity with the limits of detection (LODs) at 5.5 μg L(-1)and 10.0 μg L(-1) for 4-nitrophenol and 2-naphthol, respectively. Good linearity over the concentration ranges of 24-384 μg L(-1) for 4-nitrophenol and 28-336 μg L(-1) for 2-naphthol was obtained with correlation coefficients of 0.9998 and 0.9961, respectively. The proposed method can directly extract acidic compound from environmental sample or even more complex sample matrix without any pH adjustment procedure. Copyright © 2014 Elsevier B.V. All rights reserved.

SO2 Solvation in the 1-Ethyl-3-Methylimidazolium Thiocyanate Ionic Liquid by Incorporation into the Extended Cation-Anion Network.

PubMed

Firaha, Dzmitry S; Kavalchuk, Mikhail; Kirchner, Barbara

We have carried out an ab initio molecular dynamics study on the sulfur dioxide (SO 2 ) solvation in 1-ethyl-3-methylimidazolium thiocyanate for which we have observed that both cations and anions play an essential role in the solvation of SO 2 . Whereas, the anions tend to form a thiocyanate- and much less often an isothiocyanate-SO 2 adduct, the cations create a "cage" around SO 2 with those groups of atoms that donate weak interactions like the alkyl hydrogen atoms as well as the heavy atoms of the [Formula: see text]-system. Despite these similarities between the solvation of SO 2 and CO 2 in ionic liquids, an essential difference was observed with respect to the acidic protons. Whereas CO 2 avoids accepting hydrogen bonds form the acidic hydrogen atoms of the cations, SO 2 can from O(SO 2 )-H(cation) hydrogen bonds and thus together with the strong anion-adduct it actively integrates in the hydrogen bond network of this particular ionic liquid. The fact that SO 2 acts in this way was termed a linker effect by us, because the SO 2 can be situated between cation and anion operating as a linker between them. The particular contacts are the H(cation)[Formula: see text]O(SO 2 ) hydrogen bond and a S(anion)-S(SO 2 ) sulfur bridge. Clearly, this observation provides a possible explanation for the question of why the SO 2 solubility in these ionic liquids is so high.

Physical chemistry and evolution of salt tolerance in halobacteria

NASA Technical Reports Server (NTRS)

Lanyi, J. K.

1980-01-01

The cellular constituents of extremely halophilic bacteria not only tolerate high salt concentration, but in many cases require it for optical functioning. The characteristics affected by salt include enzyme activity, stability, allosteric regulation, conformation and subunit association. The salt effects are of two major kinds: electrostatic shielding of negative charges by cations at low salt concentration, and hydrophobic stabilization by salting-out type salts at high salt concentration. The composition of halobacterial proteins shows an excess of acidic amino acids and a deficiency of nonpolar amino acids, which accounts for these effects. Since the cohesive forces are weaker and the repulsing forces are stronger in these proteins, preventing aggregation in salt, these structures are no longer suited for functioning in the absence of high salt concentrations. Unlike these nonspecific effects, ribosomes in halobacteria show marked preference for potassium over sodium ions. To ensure the proper intracellular ionic composition, powerful ion transport systems have evolved in the halobacteria, resulting in the extrusion of sodium ions and their replacement by potassium. It is likely that such membrane transport system for ionic movements is a necessary requisite for salt tolerance.

Ion-exclusion/cation-exchange chromatography with dual detection of the conductivity and spectrophotometry for the simultaneous determination of common inorganic anionic species and cations in river and wastewater.

PubMed

Nakatani, Nobutake; Kozaki, Daisuke; Mori, Masanobu; Hasebe, Kiyoshi; Nakagoshi, Nobukazu; Tanaka, Kazuhiko

2011-01-01

Simultaneous determinations of common inorganic anionic species (SO(4)(2-), Cl(-), NO(3)(-), phosphate and silicate) and cations (Na(+), NH(4)(+), K(+), Mg(2+) and Ca(2+)) were conducted using an ion-chromatography system with dual detection of conductivity and spectrophotometry in tandem. The separation of ionic species on a weakly acidic cation-exchange resin was accomplished using a mixture of 100 mM ascorbic acid and 4 mM 18-crown-6 as an acidic eluent (pH 2.6), after which the ions were detected using a conductivity detector. Subsequently, phosphate and silicate were analyzed based on derivatization with molybdate and spectrophotometry at 700 nm. The detection limits at S/N = 3 ranged from 0.11 to 2.9 µM for analyte ionic species. This method was applied to practical river water and wastewater with acceptable criteria for the anion-cation balance and comparisons of the measured and calculated electrical conductivity, demonstrating the usefulness of the present method for water quality monitoring.

Distinct Effects of Humic Acid on Transport and Retention of TiO2 Rutile Nanoparticles in Saturated Sand Columns

EPA Science Inventory

The distinct effects of humic acid (HA, 0−10 mg L−1) on the transport of titanium dioxide (rutile) nanoparticles (nTiO2) through saturated sand columns were observed under conditions of environmental relevance (ionic strength 3−200 mM NaCl, pH 5.7 and 9.0). Specifically, the tra...

Chemical and thermal stability of N-heterocyclic ionic liquids in catalytic C-H activation reactions.

PubMed

Chen, Guanyi; Kang, Shujuan; Ma, Qisheng; Chen, Weiqun; Tang, Yongchun

2014-11-01

(1)H-NMR spectrum analyses are applied to study the chemical and thermal stability of selected N-heterocyclic ionic liquids within the reaction system that can highly efficiently activate a C-H bond of methane and convert it into the C-O bond in methanol. Our results indicate that under such reaction conditions involving using a powerful Pt-based catalyst and strong acidic solvent, the aromatic ring of an imidazolium cation becomes unstable generating an ammonium ion (NH(4)(+)). Our results also suggest that the instability of the imidazolium ring is more chemically (participation in reactions) than thermally based. Modifications of the aromatic ring structure such as pyrazolium and triazolium cations can increase the chemical/thermal stability of ionic liquids under these reaction conditions. Copyright © 2014 John Wiley & Sons, Ltd.

High-throughput approach for the identification of anilinium-based ionic liquids that are suitable for electropolymerisation.

PubMed

Abdelhamid, Muhammad E; Murdoch, Timothy; Greaves, Tamar L; O'Mullane, Anthony P; Snook, Graeme A

2015-07-21

We report the synthesis of new protic ionic liquids (PILs) based on aniline derivatives and the use of high-throughput (HT) techniques to screen possible candidates. In this work, a simple HT method was applied to rapidly screen different aniline derivatives against different acids in order to identify possible combinations that produce PILs. This was followed by repeating the HT process with a Chemspeed robotic synthesis platform for more accurate results. One of the successful combinations were then chosen to be synthesised on a larger scale for further analysis. The new PILs are of interest to the fields of ionic liquids, energy storage and especially, conducting polymers as they serve as solvents, electrolytes and monomers at the same time for possible electropolymerisation (i.e. a self-contained polymer precursor).

Long-Term Experimental Determination of Solubilities of Micro-Crystalline Nd(III) Hydroxide in High Ionic Strength Solutions: Applications to Nuclear Waste Management [A Pitzer Model for Am(III)/Nd(III) hydroxide solubility in NaCl-H 2O at 298.15 K to high ionic strengths: Experimental validation and model applications

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

Xiong, Yongliang; Kirkes, Leslie Dawn; Marrs, Cassandra

In this paper, the experimental results from long-term solubility experiments on micro crystalline neodymium hydroxide, Nd(OH) 3(micro cr), in high ionic strength solutions at 298.15 K under well-constrained conditions are presented. The starting material was synthesized according to a well-established method in the literature. In contrast with the previous studies in which hydrogen ion concentrations in experiments were adjusted with addition of either an acid or a base, the hydrogen ion concentrations in our experiments are controlled by the dissolution of Nd(OH) 3(micro cr), avoiding the possibility of phase change.

Long-Term Experimental Determination of Solubilities of Micro-Crystalline Nd(III) Hydroxide in High Ionic Strength Solutions: Applications to Nuclear Waste Management [A Pitzer Model for Am(III)/Nd(III) hydroxide solubility in NaCl-H 2O at 298.15 K to high ionic strengths: Experimental validation and model applications

DOE PAGES

Xiong, Yongliang; Kirkes, Leslie Dawn; Marrs, Cassandra

2017-12-01

In this paper, the experimental results from long-term solubility experiments on micro crystalline neodymium hydroxide, Nd(OH) 3(micro cr), in high ionic strength solutions at 298.15 K under well-constrained conditions are presented. The starting material was synthesized according to a well-established method in the literature. In contrast with the previous studies in which hydrogen ion concentrations in experiments were adjusted with addition of either an acid or a base, the hydrogen ion concentrations in our experiments are controlled by the dissolution of Nd(OH) 3(micro cr), avoiding the possibility of phase change.

Extending the diffuse layer model of surface acidity behavior: I. Model development

EPA Science Inventory

Considerable disenchantment exists within the environmental research community concerning our current ability to accurately model surface-complexation-mediated low-porewater-concentration ionic contaminant partitioning with natural surfaces. Several authors attribute this unaccep...

Chemistry Notes

ERIC Educational Resources Information Center

School Science Review, 1972

1972-01-01

Short articles describing the construction of a self-testing device for learning ionic formulae, problems with standard'' experiments in crystallizing sulfur, preparative details for a cold-setting adhesive and vermillion dye, and providing data related to the industrial manufacture of sulphuric acid. (AL)

Simultaneous determination of Magnolol and Honokiol by amino acid ionic liquid synchronous fluorescence spectrometry

NASA Astrophysics Data System (ADS)

Liu, Wei; Zhu, Xiashi

2018-05-01

A novel method based on amino acid ionic liquids (AAILs) as an additive synchronous fluorescence spectrometry is proposed for simultaneous determination of magnolol (MN) and honokiol (HN) in traditional Chinese medicine Houpu. The overlapping fluorescence spectrum of MN and HN could be completely separated in the AAILs medium. Experiment parameters (the type and concentration of AAILs, pH values and temperature) were discussed. The detection limits of MN and HN reached 1.46 ng/mL, 0.92 ng/mL and the recovery rates ranged from 98.6%-100.7%, 99.7%-100.6%, respectively. This methods was successfully employed for simultaneously determination of MN and HN in real samples. No significant differences could be found in the results of this method and the pharmacopoeia of People's Republic of China 2015 (Ch.P.2015). The experiment mechanisms were discussed by the Gaussian simulation and fluorescence quantum yield.

Aqueous solutions of acidic ionic liquids for enhanced stability of polyoxometalate-carbon supercapacitor electrodes

NASA Astrophysics Data System (ADS)

Hu, Chenchen; Zhao, Enbo; Nitta, Naoki; Magasinski, Alexandre; Berdichevsky, Gene; Yushin, Gleb

2016-09-01

Nanocomposites based on polyoxometalates (POMs) nanoconfined in microporous carbons have been synthesized and used as electrodes for supercapacitors. The addition of the pseudocapacitance from highly reversible redox reaction of POMs to the electric double-layer capacitance of carbon lead to an increase in specific capacitance of ∼90% at 1 mV s-1. However, high solubility of POM in traditional aqueous electrolytes leads to rapid capacity fading. Here we demonstrate that the use of aqueous solutions of protic ionic liquids (P-IL) as electrolyte instead of aqueous sulfuric acid solutions offers an opportunity to significantly improve POM cycling stability. Virtually no degradation in capacitance was observed in POM-based positive electrode after 10,000 cycles in an asymmetric capacitor with P-IL aqueous electrolyte. As such, POM-based carbon composites may now present a viable solution for enhancing energy density of electrical double layer capacitors (EDLC) based on pure carbon electrodes.

Mucopolysaccharides in aqueous solutions: effect of ionic strength on titration curves.

PubMed

Rueda, C; Arias, C; Galera, P; López-Cabarcos, E; Yagüe, A

2001-01-01

We study the changes taking place in hyaluronic acid, chondroitin 4-sulfate (C4-S) and condroitin 6-sulfate (C6-S), at ionic strengths of 0.10, 0.15, and 0.20 in NaCl, in a neutralization process in aqueous solution. We apply the equation of Henderson Hasselbalch modified for polyelectrolytes and evaluate the changes in the electrostatic free energy starting from the pK curves as a function of the dissociation degree. For a dissociation degree next to 0.4 corresponding to the -COOH group of the hyaluronic acid, we observed a change in the conformation of the three glycosaminoglycans studied. This conformational change takes place as a consequence of the break of intramolecular links and the beginning of the ionization process. The macromolecules in solution show a structure of random coil sufficiently expanded so that the interaction among the close ionizable groups is negligible.

Bactericidal activity of LFchimera is stronger and less sensitive to ionic strength than its constituent lactoferricin and lactoferrampin peptides.

PubMed

Bolscher, Jan G M; Adão, Regina; Nazmi, Kamran; van den Keybus, Petra A M; van 't Hof, Wim; Nieuw Amerongen, Arie V; Bastos, Margarida; Veerman, Enno C I

2009-01-01

The innate immunity factor lactoferrin harbours two antimicrobial moieties, lactoferricin and lactoferrampin, situated in close proximity in the N1 domain of the molecule. Most likely they cooperate in many of the beneficial activities of lactoferrin. To investigate whether chimerization of both peptides forms a functional unit we designed a chimerical structure containing lactoferricin amino acids 17-30 and lactoferrampin amino acids 265-284. The bactericidal activity of this LFchimera was found to be drastically stronger than that of the constituent peptides, as was demonstrated by the need for lower dose, shorter incubation time and less ionic strength dependency. Likewise, strongly enhanced interaction with negatively charged model membranes was found for the LFchimera relative to the constituent peptides. Thus, chimerization of the two antimicrobial peptides resembling their structural orientation in the native molecule strikingly improves their biological activity.

Effect of Boron Clusters on the Ignition Reaction of HNO3 and Dicynanamide-Based Ionic Liquids.

PubMed

Schmidt, Michael W; Gordon, Mark S

2017-10-19

Many ionic liquids containing the dicynamide anion (DCA - , formula N(CN) 2 - ) exhibit hypergolic ignition when exposed to the common oxidizer nitric acid. However, the ignition delay is often about 10 times longer than the desired 5 ms for rocket applications, so that improvements are desired. Experiments in the past decade have suggested both a mechanism for the early reaction steps and also that additives such as decaborane can reduce the ignition delay. The mechanisms for reactions of nitric acid with both DCA - and protonated DCAH are considered here, using accurate wave function methods. Complexation of DCA - or DCAH with borane clusters B 10 H 14 or B 9 H 14 - is found to modify these mechanisms slightly by changing the nature of some of the intermediate saddle points and by small reductions in the reaction barriers.

The Effect of Microporous Polymeric Support Modification on Surface and Gas Transport Properties of Supported Ionic Liquid Membranes.

PubMed

Akhmetshina, Alsu A; Davletbaeva, Ilsiya M; Grebenschikova, Ekaterina S; Sazanova, Tatyana S; Petukhov, Anton N; Atlaskin, Artem A; Razov, Evgeny N; Zaripov, Ilnaz I; Martins, Carla F; Neves, Luísa A; Vorotyntsev, Ilya V

2015-12-30

Microporous polymers based on anionic macroinitiator and toluene 2,4-diisocyanate were used as a support for 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF₆]) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([emim][Tf₂N]) immobilization. The polymeric support was modified by using silica particles associated in oligomeric media, and the influence of the modifier used on the polymeric structure was studied. The supported ionic liquid membranes (SILMs) were tested for He, N₂, NH₃, H₂S, and CO₂ gas separation and ideal selectivities were calculated. The high values of ideal selectivity for ammonia-based systems with permanent gases were observed on polymer matrixes immobilized with [bmim][PF₆] and [emim][Tf₂N]. The modification of SILMs by nanosize silica particles leads to an increase of NH₃ separation relatively to CO₂ or H₂S.

Ion-mediated enhancement of xylem hydraulic conductivity in four Acer species: relationships with ecological and anatomical features.

PubMed

Nardini, Andrea; Dimasi, Federica; Klepsch, Matthias; Jansen, Steven

2012-12-01

The 'ionic effect', i.e., changes in xylem hydraulic conductivity (k(xyl)) due to variation of the ionic sap composition in vessels, was studied in four Acer species growing in contrasting environments differing in water availability. Hydraulic measurements of the ionic effect were performed together with measurements on the sap electrical conductivity, leaf water potential and vessel anatomy. The low ionic effect recorded in Acer pseudoplatanus L. and Acer campestre L. (15.8 and 14.7%, respectively), which represented two species from shady and humid habitats, was associated with a low vessel grouping index, high sap electrical conductivity and least negative leaf water potential. Opposite traits were found for Acer monspessulanum L. and Acer platanoides L., which showed an ionic effect of 23.6 and 23.1%, respectively, and represent species adapted to higher irradiance and/or lower water availability. These findings from closely related species provide additional support that the ionic effect could function as a compensation mechanism for embolism-induced loss of k(xyl), either as a result of high evaporative demand or increased risk of hydraulic failure.

Interaction of Sodium Hyaluronate with a Biocompatible Cationic Surfactant from Lysine: A Binding Study.

PubMed

Bračič, Matej; Hansson, Per; Pérez, Lourdes; Zemljič, Lidija F; Kogej, Ksenija

2015-11-10

Mixtures of natural and biodegradable surfactants and ionic polysaccharides have attracted considerable research interest in recent years because they prosper as antimicrobial materials for medical applications. In the present work, interactions between the lysine-derived biocompatible cationic surfactant N(ε)-myristoyl-lysine methyl ester, abbreviated as MKM, and the sodium salt of hyaluronic acid (NaHA) are investigated in aqueous media by potentiometric titrations using the surfactant-sensitive electrode and pyrene-based fluorescence spectroscopy. The critical micelle concentration in pure surfactant solutions and the critical association concentration in the presence of NaHA are determined based on their dependence on the added electrolyte (NaCl) concentration. The equilibrium between the protonated (charged) and deprotonated (neutral) forms of MKM is proposed to explain the anomalous binding isotherms observed in the presence of the polyelectrolyte. The explanation is supported by theoretical model calculations of the mixed-micelle equilibrium and the competitive binding of the two MKM forms to the surface of the electrode membrane. It is suggested that the presence of even small amounts of the deprotonated form can strongly influence the measured electrode response. Such ionic-nonionic surfactant mixtures are a special case of mixed surfactant systems where the amount of the nonionic component cannot be varied independently as was the case for some of the earlier studies.

Bio-functionalization of electro-synthesized polypyrrole surface by heme enzyme using a mixture of Nafion and glutaraldehyde as synergetic immobilization matrix: Conformational characterization and electrocatalytic studies

NASA Astrophysics Data System (ADS)

ElKaoutit, Mohammed; Naranjo-Rodriguez, Ignacio; Domínguez, Manuel; Hidalgo-Hidalgo-de-Cisneros, José Luis

2011-10-01

Use of a mixture of Nafion and glutaraldehyde as new immobilization matrix was described. The percentage of Nafion was optimized to prevent denaturation of horseradish peroxidase enzyme after its crosslinkage with glutaraldehyde on electro-synthesized polypyrrole surface. Topographic study by Atomic Force Microscopy (AFM) shows that the enzyme seems to have been introduced inside the ionic cluster of Nafion. The characterization of the resulting bio-interfaces by UV-vis and FT-IR shows that the intra-crosslinkage phenomena caused by the use of glutaraldehyde can be eliminated by the optimization of the concentration of Nafion additive. The secondary structure contents of native and immobilized enzyme were analyzed by a Gaussian curve fitting of the respective FT-IR spectra in the amide I region. Immobilized enzyme presented notable increasing percentages of globular and short helical structure compared with native enzyme. This indicates that immobilized enzyme was folded which is in accordance with AFM studies and supports the enzyme entrance inside ionic clutter of Nafion. Thanks to synergic effects of the polypyrrole conducting polymer and the perfluorosulfonic acid polymer Nafion, HRP enzyme was immobilized in its "native" state, the resulting biosensor was able to sense peroxide without any chemical mediator and can be categorized as third generation.

Dicationic ionic liquid mediated fabrication of Au@Pt nanoparticles supported on reduced graphene oxide with highly catalytic activity for oxygen reduction and hydrogen evolution

NASA Astrophysics Data System (ADS)

Shi, Ya-Cheng; Chen, Sai-Sai; Feng, Jiu-Ju; Lin, Xiao-Xiao; Wang, Weiping; Wang, Ai-Jun

2018-05-01

Ionic liquids as templates or directing agents have attracted great attention for shaping-modulated synthesis of advanced nanomaterials. In this work, reduced graphene oxide supported uniform core-shell Au@Pt nanoparticles (Au@Pt NPs/rGO) were fabricated by a simple one-pot aqueous approach, using N-methylimidazolium-based dicationic ionic liquid (1,1-bis(3-methylimadazoilum-1-yl)butylene bromide, [C4(Mim)2]2Br) as the shape-directing agent. The morphology evolution, structural information and formation mechanism of Au@Pt NPs anchored on rGO were investigated by a series of characterization techniques. The obtained nanocomposites displayed superior electrocatalytic features toward hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) compared with commercial Pt/C catalyst. This approach provides a novel route for facile synthesis of nanocatalysts in fuel cells.

Modeling solubility and acid-base properties of some amino acids in aqueous NaCl and (CH3)4NCl aqueous solutions at different ionic strengths and temperatures.

PubMed

Bretti, Clemente; Giuffrè, Ottavia; Lando, Gabriele; Sammartano, Silvio

2016-01-01

New potentiometric experiments have been performed in NaCl and in (CH3)4NCl media, to determine the protonation constants, the protonation enthalpy changes and the solubility of six natural α-amino acids, namely Glycine (Gly), Alanine (Ala), Valine (Val), Leucine (Leu), Serine (Ser) and Phenylalanine (Phe). The aim of the work is the rationalization of the protonation thermodynamics (log [Formula: see text], solubility and [Formula: see text]) in NaCl, determining recommended, tentative or provisional values in selected experimental conditions and to report, for the first time, data in a weak interacting medium, as (CH3)4NCl. Literature data analysis was performed selecting the most reliable values, analyzed together with new data here reported. Significant trends and similarities were observed in the behavior of the six amino acids, and in some cases it was possible to determine common parameters for the ionic strength and temperature dependence. In general, the first protonation step, relative to the amino group, is significantly exothermic (average value is [Formula: see text] = -44.5 ± 0.4 kJ mol(-1) at infinite dilution and T = 298.15 K), and the second, relative to the carboxylate group, is fairly close to zero ([Formula: see text] = -2.5 ± 1.6, same conditions). In both cases, the main contribution to the proton binding reaction is mainly entropic in nature. For phenylalanine and leucine, solubility measurements at different concentrations of supporting electrolyte allowed to determine total and specific solubility values, then used to obtain the Setschenow and the activity coefficients of all the species involved in the protonation equilibria. The values of the first protonation constant in (CH3)4NCl are lower than the corresponding values in NaCl, due to the weak interaction between the deprotonated amino group and (CH3)4N(+). In this light, differences between the protonation functions in NaCl and (CH3)4NCl were used for the quantification of the stability of the weak [(CH3)4N(+)-L(-)] complexes that resulted log K = -0.38 ± 0.07 as an average value for the six amino acids.

Prominent roles of impurities in ionic liquid for catalytic conversion of carbohydrates

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

Zhao, Haibo; Brown, Heather M.; Holladay, Johnathan E.

2012-02-07

In the last two decades, ionic liquids have emerged as new and versatile solvents, and many of them are also catalysts for a broad range of catalytic reactions. Certain ionic liquids have been found to possess the unique capability of dissolving cellulosic biomass. The potential of such ionic liquids as solvent to enable catalytic conversion of cellulosic polymers was first explored and demonstrated by Zhao et al. This field of research has since experienced a rapid growth. Most ionic liquids have negligible vapor pressure and excellent thermal stability over a wide temperature range. For example, ionic liquids composed of 1-ethyl-3-methylimidazoliummore » (EMIM+) cation and Cl- anion was reported to be stable up to 285 C, while salts of the same cation with other anions such as BF4- and PF6- are thermally stable above 380 C under inert atmosphere. It is well known that presence of impurities in ionic liquids typically causes changes in physical properties, e.g. decreasing in melting point and viscosity. Addition of Lewis acidic metal chlorides, e.g. AlCl3 to 1-alkyl-3-methylimidazolium chloride, [AMIM]Cl, is an exothermic reaction and considerably reduces the melting point by forming [AMIM]AlCl4 or [AMIM]Al2Cl7 that are also ionic liquids but have much lower melting point than the parent [AMIM]Cl. While most early research on catalysis of ionic liquids involving metallohalide anions were typically conducted from stoichiometric ratio of such anions to organic cations, e.g. [AMIM]+, the use of pure ionic liquids only as a solvent to carry out catalysis by a catalytic amount of a metal halide as catalyst truly displayed the solvent property of such ionic liquids.4 In such reaction systems, catalytic amounts of metal halides were used to catalyze the conversion of glucose and cellulose.4,11,12 The metal chloride catalyst concentration was in the order of 10-3 M. The presence of another metal chloride in the ionic liquids, even in the order of 10-5 M concentration was found to bring a dramatic synergistic effect. Therefore, the catalytic performance of the metal halide catalyst for the conversion of carbohydrates in the ionic liquid systems is highly sensitive to the presence of impurities. This work presents findings on the role of impurities that were present in some commercially available ionic liquids used for the conversion of the cellulose.« less

Design of Decorated Self-Assembling Peptide Hydrogels as Architecture for Mesenchymal Stem Cells

PubMed Central

Zamuner, Annj; Cavo, Marta; Scaglione, Silvia; Messina, Grazia Maria Lucia; Russo, Teresa; Gloria, Antonio; Marletta, Giovanni; Dettin, Monica

2016-01-01

Hydrogels from self-assembling ionic complementary peptides have been receiving a lot of interest from the scientific community as mimetic of the extracellular matrix that can offer three-dimensional supports for cell growth or can become vehicles for the delivery of stem cells, drugs or bioactive proteins. In order to develop a 3D “architecture” for mesenchymal stem cells, we propose the introduction in the hydrogel of conjugates obtained by chemoselective ligation between a ionic-complementary self-assembling peptide (called EAK) and three different bioactive molecules: an adhesive sequence with 4 Glycine-Arginine-Glycine-Aspartic Acid-Serine-Proline (GRGDSP) motifs per chain, an adhesive peptide mapped on h-Vitronectin and the growth factor Insulin-like Growth Factor-1 (IGF-1). The mesenchymal stem cell adhesion assays showed a significant increase in adhesion and proliferation for the hydrogels decorated with each of the synthesized conjugates; moreover, such functionalized 3D hydrogels support cell spreading and elongation, validating the use of this class of self-assembly peptides-based material as very promising 3D model scaffolds for cell cultures, at variance of the less realistic 2D ones. Furthermore, small amplitude oscillatory shear tests showed that the presence of IGF-1-conjugate did not alter significantly the viscoelastic properties of the hydrogels even though differences were observed in the nanoscale structure of the scaffolds obtained by changing their composition, ranging from long, well-defined fibers for conjugates with adhesion sequences to the compact and dense film for the IGF-1-conjugate. PMID:28773852

Solid-state supercapacitors with ionic liquid based gel polymer electrolyte: Effect of lithium salt addition

NASA Astrophysics Data System (ADS)

Pandey, G. P.; Hashmi, S. A.

2013-12-01

Performance characteristics of the solid-state supercapacitors fabricated with ionic liquid (IL) incorporated gel polymer electrolyte and acid treated multiwalled carbon nanotube (MWCNT) electrodes have been studied. The effect of Li-salt (LiPF6) addition in the IL (1-ethyl-3-methylimidazolium tris(pentafluoroethyl) trifluorophosphate, EMImFAP) based gel electrolyte on the performance of supercapacitors has been specifically investigated. The LiPF6/IL/poly(vinylidine fluoride-co-hexafluoropropylene) (PVdF-HFP) gel electrolyte film possesses excellent electrochemical window of 4 V (from -2.0 to 2.0 V), high ionic conductivity ∼2.6 × 10-3 S cm-1 at 20 °C and high enough thermal stability. The comparative performance of supercapacitors employing electrolytes with and without lithium salt has been evaluated by impedance spectroscopy and cyclic voltammetric studies. The acid-treated MWCNT electrodes show specific capacitance of ∼127 F g-1 with IL/LiPF6 containing gel polymer electrolyte as compared to that with the gel polymer electrolyte without Li-salt, showing the value of ∼76 F g-1. The long cycling stability of the solid state supercapacitor based on the Li-salt containing gel polymer electrolyte confirms the electrochemical stability of the electrolyte.

Polymer Micelles with Cross-Linked Polyanion Core for Delivery of a Cationic Drug Doxorubicin

PubMed Central

Kim, Jong Oh; Kabanov, Alexander V.; Bronich, Tatiana K.

2009-01-01

Polymer micelles with cross-linked ionic cores were prepared by using block ionomer complexes of poly(ethylene oxide)-b-poly(methacrylic acid) (PEO-b-PMA) copolymer and divalent metal cations as templates. Doxorubicin (DOX), an anthracycline anticancer drug, was successfully incorporated into the ionic cores of such micelles via electrostatic interactions. A substantial drug loading level (up to 50 w/w %) was achieved and it was strongly dependent on the structure of the cross-linked micelles and pH. The drug-loaded micelles were stable in aqueous dispersions exhibiting no aggregation or precipitation for a prolonged period of time. The DOX-loaded polymer micelles exhibited noticeable pH-sensitive behavior with accelerated release of DOX in acidic environment due to the protonation of carboxylic groups in the cores of the micelles. The attempt to protect the DOX-loaded core with the polycationic substances resulted in the decrease of loading efficacy and had a slight effect on the release characteristics of the micelles. The DOX-loaded polymer micelles exhibited a potent cytotoxicity against human A2780 ovarian carcinoma cells. These results point to a potential of novel polymer micelles with cross-linked ionic cores to be attractive carriers for the delivery of DOX. PMID:19386272

Adsorption of aquatic humic substances on colloidal-size aluminum oxide particles: Influence of solution chemistry

NASA Astrophysics Data System (ADS)

Schlautman, Mark A.; Morgan, James J.

1994-10-01

The adsorption of Suwannee River humic substances (HS) on colloidal-size aluminum oxide particles was examined as a function of solution chemistry. The amount of humic acid (HA) or fulvic acid (FA) adsorbed decreased with increasing pH for all solutions of constant ionic strength. In NaCl solutions at fixed pH values, the adsorption of HA and FA increased with increasing ionic strength. The presence of Ca 2+ enhanced the adsorption of HA but had little effect on FA. For identical solution conditions, the amount (by mass) of HA adsorbed to alumina was always greater than FA. Adsorption densities for both HA and FA showed good agreement with the Langmuir equation, and interpretations of adsorption processes were made from the model parameters. For FA, ligand exchange appears to be the dominant adsorption reaction for the conditions studied here. Ligand exchange is also a major adsorption reaction for HA; however, other reactions contribute to adsorption for some solution compositions. At high pH, cation and water bridging become increasingly important for HA adsorption with increasing amounts of Na + and Ca 2+, respectively. At low to neutral pH values, increases in these same two cations make hydrophobic bonding more effective. Calculations of HS carboxyl group densities in the adsorbed layer support the proposed adsorption reactions. From the adsorption data it appears that fewer than 3.3 HS-COO - groups per nm 2 can be bound directly as inner-sphere complexes by the alumina surface. We propose that the influence of aqueous chemistry on HS adsorption reactions, and therefore on the types of HS surface complexes formed, affects the formation and nature of organic coatings on mineral surfaces.

Computational analysis of the solvation of coffee ingredients in aqueous ionic liquid mixtures† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6ra24736a Click here for additional data file.

PubMed Central

Zeindlhofer, Veronika; Khlan, Diana; Bica, Katharina

2017-01-01

In this paper, we investigate the solvation of coffee ingredients including caffeine, gallic acid as representative for phenolic compounds and quercetin as representative for flavonoids in aqueous mixtures of the ionic liquid 1-ethyl-3-methylimidazolium acetate [C2mim][OAc] at various concentrations. Due to the anisotropy of the solutes we show that classical Kirkwood–Buff theory is not appropriate to study solvation effects with increasing ionic liquid content. However, excess coordination numbers as well as the mean residence time of solvent molecules at the surface of the solutes can be determined by Voronoi tessellation. Since the volume of the hydration shells is also available by this method, solvation free energies will be discussed as a function of the ionic liquid concentration to yield a physical meaningful picture of solvation for the anisotropic solutes. Hydrogen bonding capabilities of the solutes and their relevance for experimental extraction yields from spent coffee grounds are also discussed. PMID:28496974

Exploring the role of ionic liquids to tune the polymorphic outcome of organic compounds.

PubMed

Zeng, Qingying; Mukherjee, Arijit; Müller, Peter; Rogers, Robin D; Myerson, Allan S

2018-02-14

While molecular solvents are commonly used in the screening of polymorphs, the choices are often restricted. Ionic liquids (ILs) - also referred as designer solvents - have immense possibility in this regard because of their wide flexibility of tunability. More importantly, the interactions among the IL components are completely unique compared to those present in the molecular solvents. In this context, we have chosen tetrolic acid (TA) and isonicotinamide (INA), which showed solution-structure link in molecular solvents in the past, as probes to investigate the role of imidazolium based ionic liquids in the polymorphism of these two systems and whether the different solute-solvent interactions in ILs affect the polymorphic outcome. It is observed that the selected imidazolium-based ILs, with varying anion basicity have influenced the crystallization outcome by the interaction between ILs and model compounds. Later, we have utilized the concept of double salt ionic liquids (DSIL) for INA, a penta-morphic system, to investigate the variation in the polymorphic outcome. This approach helped to obtain the forms that were otherwise inaccessible in ILs.

Temperature-dependent gel-type ionic liquid compounds based on vanadium-substituted polyoxometalates with Keggin structure.

PubMed

Huang, Tianpei; Xie, Zhirong; Wu, Qingyin; Yan, Wenfu

2016-03-07

A series of temperature-dependent gel-type ionic liquid compounds have been synthesized from 1-(3-sulfonic group) propyl-3-methyl imidazolium (abbreviated as MIMPS) and three vanadium-substituted heteropoly acids H5SiW11VO40, H5SiMo11VO40 and H7SiW9V3O40. The designed and synthesized gel-type polyoxometalate ionic liquids (POM-ILs) have demonstrated a tendency to exhibit a layered structure. Moreover, they can undergo a phase transformation from a viscous gel-state to a liquid-state below 100 °C, and ionic conductivity up to 10(-3) S cm(-1) was observed at 120 °C. Cyclic voltammetry was carried out to study their electrochemical properties in organic solutions, and it was found that the oxidizability of the three POM-ILs decreases in the order: [MIMPS]7SiW9V3O40 > [MIMPS]5SiMo11VO40 > [MIMPS]5SiW11VO40. This result indicates that the redox behavior can be tuned by changing the chemical composition of the heteropolyanions.

The pH of chemistry assays plays an important role in monoclonal immunoglobulin interferences.

PubMed

Alberti, Michael O; Drake, Thomas A; Song, Lu

2015-12-01

Immunoglobulin paraproteins can interfere with multiple chemistry assays. We want to investigate the mechanisms of immunoglobulin interference. Serum samples containing paraproteins from the index patient and eight additional patients were used to investigate the interference with the creatinine and total protein assays on the Beckman Coulter AU5400/2700 analyzer, and to determine the effects of pH and ionic strength on the precipitation of different immunoglobulins in these patient samples. The paraprotein interference with the creatinine and total protein assays was caused by the precipitation of IgM paraprotein in the index patient's samples under alkaline assay conditions. At extremely high pH (12-13) and extremely low pH (1-2) and low ionic strength, paraprotein formed large aggregates in samples from the index patient but not from other patients. The pH and ionic strength are the key factors that contribute to protein aggregation and precipitation which interfere with the creatinine and total protein measurements on AU5400/2700. The different amino acid sequence of each monoclonal paraprotein will determine the pH and ionic strength at which the paraprotein will precipitate.

Synthesis and characterization of ionic polymer networks in a room-temperature ionic liquid.

PubMed

Stanzione, Joseph F; Jensen, Robert E; Costanzo, Philip J; Palmese, Giuseppe R

2012-11-01

Ionic liquid gels (ILGs) for potential use in ion transport and separation applications were generated via a free radical copolymerization of 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) and N,N'-methylene(bis)acrylamide (MBA) using 1-ethyl-3-methylimidazolium ethylsulfate (IL) as a room temperature ionic liquid solvent medium. The AMPS and MBA monomer solubility window in the IL in the temperature range of 25 to 65 °C was determined. In situ ATR-FTIR showed near complete conversion of monomers to a cross-linked polymer network. ILGs with glass transition temperatures (T(g)s) near -50 °C were generated with T(g) decreasing with increasing IL content. The elastic moduli in compression (200 to 6600 kPa) decreased with increasing IL content and increasing AMPS content while the conductivities (0.35 to 2.14 mS cm⁻¹) increased with increasing IL content and decreasing MBA content. The polymer-IL interaction parameter (χ) (0.48 to 0.55) was determined via a modified version of the Bray and Merrill equation.

Development of new ionic gelation strategy: Towards the preparation of new monodisperse and stable hyaluronic acid/β-cyclodextrin-grafted chitosan nanoparticles as drug delivery carriers for doxorubicin

NASA Astrophysics Data System (ADS)

Mihoub, Amina Ben; Saidat, Boubakeur; Bal, Youssef; Frochot, Céline; Vanderesse, Régis; Acherar, Samir

2018-03-01

In the present study, β-cyclodextrin-grafted chitosan nanoparticles (β-CD- g-CS NPs) were prepared using a new ionic gelation strategy involving a synergistic effect of NaCl (150 mmol/L), 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES, 10 mmol/L), and water bath sonication. This new strategy afforded smaller and more monodisperse β-CD- g-CS NPs vs. the classical ionic gelation method. New HA/β-CD- g-CS NPs were also prepared using the above-mentioned strategy by adding hyaluronic acid (HA) to the β-CD- g-CS copolymer at different weight ratios until the ZP values conversion. The best result was obtained with the weight ratio of w(HA): w(β-CD- g-CS) = 2:1 and furnished new spherical and smooth HA/β-CD- g-CS NPs. Furthermore, the stability of β- CD- g-CS NPs and HA/β-CD- g-CS NPs at 4°C in physiological medium (pH 7.4) was compared for 3 weeks period and showed that HA/β-CD- g-CS NPs were more stable all maintaining their monodispersity and high negative ZP values compared to β-CD- g-CS NPs. Finally, preliminary study of HA/β-CD- g-CS NPs as carrier for the controlled release of the anticancer drug doxorubicin was investigated. These new HA/β-CD- g-CS NPs can potentially be used as drug delivery and targeting systems for cancer treatment.

Label-free electrical quantification of amplified nucleic acids through nanofluidic diodes.

PubMed

Liu, Yifan; Yobas, Levent

2013-12-15

A label-free method of quantifying nucleic acids in polymerase chain reaction (PCR) is described and could be the basis for miniaturized devices that can amplify and detect target nucleic acids in real time. The method takes advantage of ionic current rectification effect discovered in nanofluidic channels exhibiting a broken symmetry in electrochemical potential - nanofluidic diodes. Nanofluidic diodes are prototyped here on nanopipettes readily pulled from individual thin-walled glass capillaries for a proof of concept demonstration yet the basic concept would be applicable to ionic rectifiers constructed through other means. When a nanopipette modified in the tip region with cationic polyelectrolytes is presented with an unpurified PCR product, the tip surface electrostatically interacts with the amplicons and modulates its ionic rectification direction in response to the intrinsic charge of those adsorbed. Modulations are gradual and correlate well with the mass concentration of the amplicons above 2.5 ng/μL, rather than their sizes, with adequate discrimination against the background. Moreover, the tip surface, following a measurement, is regenerated through a layer-by-layer assembly of cationic polyelectrolytes and amplicons. The regenerated tips are capable of measuring distinct mass concentrations without signs of noticeable degradation in sensitivity. Further, the tips are shown capable of reproducing the amplification curve of real-time PCR through sequential steps of surface regeneration and simple electrical readout during the intermediate reaction stages. This suggests that nanopipettes as nanofluidic diodes are at a capacity to be employed for monitoring the PCR progress. Copyright © 2013 Elsevier B.V. All rights reserved.

Gamma ray-induced synthesis of hyaluronic acid/chondroitin sulfate-based hydrogels for biomedical applications

NASA Astrophysics Data System (ADS)

Zhao, Linlin; Gwon, Hui-Jeong; Lim, Youn-Mook; Nho, Young-Chang; Kim, So Yeon

2015-01-01

Hyaluronic acid (HA)/chondroitin sulfate (CS)/poly(acrylic acid) (PAAc) hydrogel systems were synthesized by gamma-ray irradiation without the use of additional initiators or crosslinking agents to achieve a biocompatible hydrogel system for skin tissue engineering. HA and CS derivatives with polymerizable residues were synthesized. Then, the hydrogels composed of glycosaminoglycans, HA, CS, and a synthetic ionic polymer, PAAc, were prepared using gamma-ray irradiation through simultaneous free radical copolymerization and crosslinking. The physicochemical properties of the HA/CS/PAAc hydrogels having various compositions were investigated to evaluate their feasibility as artificial skin substitutes. The gel fractions of the HA/CS/PAAc hydrogels increased in absorbed doses up to 15 kGy, and they exhibited 91-93% gel fractions under 15 kGy radiation. All of the HA/CS/PAAc hydrogels exhibited relatively high water contents of over 90% and reached an equilibrium swelling state within 24 h. The enzymatic degradation kinetics of the HA/CS/PAAc hydrogels depended on both the concentration of the hyaluronidase solution and the ratio of HA/CS/PAAc. The in vitro drug release profiles of the HA/CS/PAAc hydrogels were significantly influenced by the interaction between the ionic groups in the hydrogels and the ionic drug molecules as well as the swelling of the hydrogels. From the cytotoxicity results of human keratinocyte (HaCaT) cells cultured with extracts of the HA/CS/PAAc hydrogels, all of the HA/CS/PAAc hydrogel samples tested showed relatively high cell viabilities of more than 82%, and did not induce any significant adverse effects on cell viability.

Molecular dynamics simulation of amino acid ionic liquids near a graphene electrode: effects of alkyl side-chain length.

PubMed

Sadeghi Moghadam, Behnoosh; Razmkhah, Mohammad; Hamed Mosavian, Mohammad Taghi; Moosavi, Fatemeh

2016-12-07

Electric double layer (EDL) supercapacitors, using ionic liquid electrolytes, have been receiving a great deal of attention in response to the growing demand for energy storage systems. In the present study, the nanoscopic structure of amino acid ionic liquids (AAILs) as biodegradable electrolytes near a neutral graphene surface was studied by molecular dynamics (MD) simulation. In order to explore the influence of the anion type and structure, the effect of the alkyl side-chain length of amino acids on the EDL was investigated. The results for the AAILs, composed of 1-ethyl-3-methylimidazolium ([EMIM]) cations near alanine ([ALA]) and isoleucine ([ILE]) anions, were compared to a conventional electrolyte, [EMIM][PF 6 ]. A lower mobility of AAIL compared to [EMIM][PF 6 ], with diffusions as low as 10 -11 m 2 s -1 , was observed. The structural results demonstrated a layered structure near the surface and most of the adsorbed imidazolium cation rings lay flat on the graphene surface. Both MD and quantum computations were performed to shed light on the charge behavior of AAIL electrolytes. As the current results demonstrate, an increase in the anion side-chain length leads to a decrease in both the number of adsorbed ions on the surface and the thickness of the first adsorbed layer. More impressively, it was observed that a low charge concentration in the EDL of AAILs is due to more side-side interactions. This remarkable feature could introduce AAILs as more efficient electrolyte materials than conventional [EMIM][PF 6 ].

[Application of simultaneous determination of inorganic ionic species by advanced ion chromatography for water quality monitoring of river water and wastewater].

PubMed

Nakatani, Nobutake; Kozaki, Daisuke; Tanaka, Kazuhiko

2012-04-01

In this study, our recent work on advanced ion chromatographic methods for the simultaneous determination of inorganic ionic species such as common anions (SO4(2-), Cl(-) and NO3(-)) and cations (Na+, NH4+, K+, Mg2+, and Ca2+), nutrients (phosphate and silicate) and hydrogen ion/alkalinity are summarized first. Then, the applications using these methods for monitoring environmental water quality are also presented. For the determination of common anions and cations with nutrients, the separation was successfully performed by a polymethacrylate-based weakly acidic cation-exchange column of TSKgel Super IC-A/C (Tosoh, 150 mm x 6.0 mm i. d.) and a mixture solution of 100 mmol/L ascorbic acid and 4 mmol/L 18-crown-6 as acidic eluent with dual detection of conductivity and spectrophotometry. For the determination of hydrogen ion/alkalinity, the separation was conducted by TSKgel ODS-100Z column (Tosoh, 150 mm x 4.5 mm i. d.) modified with lithium dodecylsulfate and an eluent of 40 mmol/L LiCl/0.1 mmol/L lithium dodecylsulfate/0.05 mmol/L H2SO4 with conductivity detector. The differences of ion concentration between untreated and treated wastewater showed the variation of ionic species during biological treatment process in a sewage treatment plant. Occurrence and distribution of water-quality conditions were related to the bioavailability and human activity in watershed. From these results, our advanced ion chromatographic methods have contributed significantly for water quality monitoring of environmental waters.

Dramatic Influence of Ionic Liquid and Ultrasound Irradiation on the Electrophilic Sulfinylation of Aromatic Compounds by Sulfinic Esters.

PubMed

Nguyen, Ngoc-Lan Thi; Vo, Hong-Thom; Duus, Fritz; Luu, Thi Xuan Thi

2017-09-04

The sulfinylation reaction of aromatic and hetero-aromatic compounds with sulfinic esters as electrophiles has been investigated in different ionic liquids and by means of different Lewis acid salts in order to get moderate to good yields of asymmetrical sulfoxides. Mixtures of 1-butyl-3-methylimidazolium chloride and aluminum chloride were found to be the most efficient and recyclable reaction framework. Ultrasound sonication appeared to be the most useful and green activation method to afford the sulfoxides in yields better than or equivalent to those obtained under the longer-lasting conventional stirring conditions.

Electrochromic Behavior of Ionically Self-Assembled Thin Films

NASA Astrophysics Data System (ADS)

Janik, J. A.; Heflin, J. R.; Marciu, D.; Miller, M. B.; Davis, R. M.

2001-03-01

Ionically self-assembled monolayers (ISAMs), fabricated by alternate adsorption of cationic and anionic components, yield exceptionally homogeneous thin films with sub-nanometer control of the thickness and relative special location of the component materials. Using organic electrochromic materials such as polyaniline, we report studies of electrochromic responses in ISAM films. Reversible changes in the absorption spectrum are observed with the application of voltages on the order of 1.0 V. Measurements are made using both liquid electrolytes and in all-solid state devices incorporating solid polyelectrolytes such as poly(2-acylamido 2-methyl propane sulfonic acid) (PAMPS).

Hydrogen fluoride capture by imidazolium acetate ionic liquid

NASA Astrophysics Data System (ADS)

Chaban, Vitaly

2015-04-01

Extraction of hydrofluoric acid (HF) from oils is a drastically important problem in petroleum industry, since HF causes quick corrosion of pipe lines and brings severe health problems to humanity. Some ionic liquids (ILs) constitute promising scavenger agents thanks to strong binding to polar compounds and tunability. PM7-MD simulations and hybrid density functional theory are employed here to consider HF capture ability of ILs. Discussing the effects and impacts of the cation and the anion separately and together, we evaluate performance of imidazolium acetate and outline systematic search guidelines for efficient adsorption and extraction of HF.

Aerosol and snow transfer processes: An investigation on the behavior of water-soluble organic compounds and ionic species.

PubMed

Barbaro, Elena; Zangrando, Roberta; Padoan, Sara; Karroca, Ornela; Toscano, Giuseppa; Cairns, Warren R L; Barbante, Carlo; Gambaro, Andrea

2017-09-01

The concentrations of water-soluble compounds (ions, carboxylic acids, amino acids, sugars, phenolic compounds) in aerosol and snow have been determined at the coastal Italian base "Mario Zucchelli" (Antarctica) during the 2014-2015 austral summer. The main aim of this research was to investigate the air-snow transfer processes of a number of classes of chemical compounds and investigate their potential as tracers for specific sources. The composition and particle size distribution of Antarctic aerosol was measured, and water-soluble compounds accounted for 66% of the PM 10 total mass concentration. The major ions Na + , Mg 2+ , Cl - and SO 4 2- made up 99% of the total water soluble compound concentration indicating that sea spray input was the main source of aerosol. These ionic species were found mainly in the coarse fraction of the aerosol resulting in enhanced deposition, as reflected by the snow composition. Biogenic sources were identified using chemical markers such as carboxylic acids, amino acids, sugars and phenolic compounds. This study describes the first characterization of amino acids and sugar concentrations in surface snow. High concentrations of amino acids were found after a snowfall event, their presence is probably due to the degradation of biological material scavenged during the snow event. Alcohol sugars increased in concentration after the snow event, suggesting a deposition of primary biological particles, such as airborne fungal spores. Copyright © 2017 Elsevier Ltd. All rights reserved.

AN EXACT METHOD FOR RELATING ZWITTERIONIC MICROSCOPIC TO MACROSCOPIC ACIDITY CONSTANTS

EPA Science Inventory

Zwitterions are aqueous solvated molecules simultaneously possessing one negatively and one positively charged site. Although electroneutral, the environmental interaction of zwitterions with other ionic species is likely to differ significantly from the behavior of comparable e...

Hydrated Cations in the General Chemistry Course.

ERIC Educational Resources Information Center

Kauffman, George B.; Baxter, John F., Jr.

1981-01-01

Presents selected information regarding the descriptive chemistry of the common metal ions and their compounds, including the concepts of process of solution, polar molecules, ionic size and charge, complex ions, coordination number, and the Bronsted-Lowry acid-base theory. (CS)

Chemistry Notes.

ERIC Educational Resources Information Center

School Science Review, 1982

1982-01-01

Discusses laboratory procedures, classroom materials, and demonstrations including: a model for metallic/ionic structures; Friedel-Crafts acylation reaction; aids to teaching crystal structure; a metal displacement project; silver recovery from fixer and silver residues; iodine sublimation; nature of acids; card models for teaching bonding; and…

Electrodialytic in-line preconcentration for ionic solute analysis.

PubMed

Ohira, Shin-Ichi; Yamasaki, Takayuki; Koda, Takumi; Kodama, Yuko; Toda, Kei

2018-04-01

Preconcentration is an effective way to improve analytical sensitivity. Many types of methods are used for enrichment of ionic solute analytes. However, current methods are batchwise and include procedures such as trapping and elution. In this manuscript, we propose in-line electrodialytic enrichment of ionic solutes. The method can enrich ionic solutes within seconds by quantitative transfer of analytes from the sample solution to the acceptor solution under an electric field. Because of quantitative ion transfer, the enrichment factor (the ratio of the concentration in the sample and to that in the obtained acceptor solution) only depends on the flow rate ratio of the sample solution to the acceptor solution. The ratios of the concentrations and flow rates are equal for ratios up to 70, 20, and 70 for the tested ionic solutes of inorganic cations, inorganic anions, and heavy metal ions, respectively. The sensitivity of ionic solute determinations is also improved based on the enrichment factor. The method can also simultaneously achieve matrix isolation and enrichment. The method was successively applied to determine the concentrations of trace amounts of chloroacetic acids in tap water. The regulated concentration levels cannot be determined by conventional high-performance liquid chromatography with ultraviolet detection (HPLC-UV) without enrichment. However, enrichment with the present method is effective for determination of tap water quality by improving the limits of detection of HPLC-UV. The standard addition test with real tap water samples shows good recoveries (94.9-109.6%). Copyright © 2017 Elsevier B.V. All rights reserved.

Fabrication of fiber supported ionic liquids and methods of use

DOEpatents

Luebke, David R; Wickramanayake, Shan

2013-02-26

One or more embodiments relates to the production of a fabricated fiber having an asymmetric polymer network and having an immobilized liquid such as an ionic liquid within the pores of the polymer network. The process produces the fabricated fiber in a dry-wet spinning process using a homogenous dope solution, providing significant advantage over current fabrication methods for liquid-supporting polymers. The fabricated fibers may be effectively utilized for the separation of a chemical species from a mixture based on the selection of the polymer, the liquid, and the solvent utilized in the dope.

A multi-stimuli responive, self-assembling, boronic acid dipeptide

DOE PAGES

Jones, Brad Howard; Martinez, Alina Marissa; Wheeler, Jill S.; ...

2015-08-11

Modification of the dipeptide of phenylalanine, FF, with a boronic acid (BA) functionality imparts unique aqueous self-assembly behavior that responds to multiple stimuli. Changes in pH and ionic strength are used to trigger hydrogelation via the formation of nanoribbon networks. Thus, we show for the first time that the binding of polyols to the BA functionality can modulate a peptide between its assembled and disassembled states.

An Advanced Approach to Simultaneous Monitoring of Multiple Bacteria in Space

NASA Technical Reports Server (NTRS)

Eggers, Mitch

1998-01-01

This interim report describes progress on the development of spacecraft-compatible methods of nucleic acid preparation and cleanup. Grantee found that performance of a widely-known protocol could be greatly enhanced by the addition of a sizing step to eliminate acids. Testing of alternative adsorptive methods is underway. Grantee also confirmed and extended observation of precipitation of DNA by condensing agents such a spermine at low ionic strength.

Measuring the state of charge of the electrolyte solution in a vanadium redox flow battery using a four-pole cell device

NASA Astrophysics Data System (ADS)

Ngamsai, Kittima; Arpornwichanop, Amornchai

2015-12-01

The decrease in the efficiency and capacity of a vanadium redox flow battery (VRB) caused by an electrolyte imbalance is an important impediment to its long-term operation. Knowing the state of charge (SOC) of an electrolyte solution can quantify the level of the electrolyte imbalance in the VRB. In this study, a four-pole cell device is devised and employed to predict the SOC. The proposed method directly measures the ionic resistance of the electrolyte solution and is sufficiently precise to be applied in real-time mode. Experimental studies on the effects of the operating current on the four-pole cell and the concentrations of vanadium and sulfuric acid in the electrolyte solution are carried out. The results show that the four-pole cell method can be utilized to measure the electrolyte SOC. The concentrations of vanadium and sulfuric acid in the electrolyte solution affect the ionic resistance of the solution. Regarding the capacity and efficiency of the VRB system, the results indicate that the electrical charge is determined from the concentration of vanadium and that the cell voltage depends on the concentration of sulfuric acid in the electrolyte solution. The decreased vanadium concentration and increased sulfuric acid concentration improves the cell voltage efficiency.

Phase Behavior and Physical Properties of New Biobased Ionic Liquid Crystals.

PubMed

Toledo Hijo, Ariel A C; Maximo, Guilherme J; Costa, Mariana C; Cunha, Rosiane L; Pereira, Jorge F B; Kurnia, Kiki A; Batista, Eduardo A C; Meirelles, Antonio J A

2017-04-13

Protic ionic liquids (PILs) have emerged as promising compounds and attracted the interest of the industry and the academy community, due to their easy preparation and unique properties. In the context of green chemistry, the use of biocompounds, such as fatty acids, for their synthesis could disclose a possible alternative way to produce ILs with a low or nontoxic effect and, consequently, expanding their applicability in biobased processes or in the development of bioproducts. This work addressed efforts to a better comprehension of the complex solid-[liquid crystal]-liquid thermodynamic equilibrium of 20 new PILs synthesized by using fatty acids commonly found in vegetable oils, as well as their rheological profile and self-assembling ability. The work revealed that their phase equilibrium and physical properties are significantly impacted by the structure of the ions used for their synthesis. The use of unsaturated fatty acids and bis(2-hydroxyethyl)ammonium for the synthesis of these biobased ILs led to a drastic decreasing of their melting temperatures. Also, the longest alkyl chain fatty acids promoted higher self-assembling and more stable mesophases. Besides their sustainable appeal, the marked high viscosity, non-Newtonian profile, and very low critical micellar concentration values of the PIL crystals here disclosed make them interesting renewable compounds with potential applications as emulsifiers, stabilizers, thickeners, or biolubricants.

Fast comprehensive two-dimensional gas chromatography method for fatty acid methyl ester separation and quantification using dual ionic liquid columns.

PubMed

Nosheen, Asia; Mitrevski, Blagoj; Bano, Asghari; Marriott, Philip J

2013-10-18

Safflower oil is a complex mixture of C18 saturated and unsaturated fatty acids amongst other fatty acids, and achieving separation between these similar structure components using one dimensional gas chromatography (GC) may be difficult. This investigation aims to obtain improved separation of fatty acid methyl esters in safflower oil, and their quantification using comprehensive two-dimensional GC (GC×GC). Here, GC×GC separation is accomplished by the coupling of two ionic liquid (IL) column phases: the combination of SLB-IL111 with IL59 column phases was finally selected since it provided excellent separation of a FAME standard mixture, as well as fatty acids in safflower and linseed oil, compared to other tested column sets. Safflower oil FAME were well separated in a short run of 16min. FAME validation was demonstrated by method reproducibility, linearity over a range up to 500mgL(-1), and limits of detection which ranged from 1.9mgL(-1) to 5.2mgL(-1) at a split ratio of 20:1. Quantification was carried out using two dilution levels of 200-fold for major components and 20-fold for trace components. The fatty acids C15:0 and C17:0 were not reported previously in safflower oil. The SLB-IL111/IL59 column set proved to be an effective and novel configuration for separation and quantification of vegetable and animal oil fatty acids. Copyright © 2013 Elsevier B.V. All rights reserved.

Investigation of the acid-base and electromigration properties of 5-azacytosine derivatives using capillary electrophoresis and density functional theory calculations.

PubMed

Geffertová, Denisa; Ali, Syed Tahir; Šolínová, Veronika; Krečmerová, Marcela; Holý, Antonín; Havlas, Zdeněk; Kašička, Václav

2017-01-06

Capillary electrophoresis (CE) and quantum mechanical density functional theory (DFT) were applied to the investigation of the acid-base and electromigration properties of important compounds: newly synthesized derivatives of 5-azacytosine - analogs of efficient antiviral drug cidofovir. These compounds exhibit a strong antiviral activity and they are considered as potential new antiviral agents. For their characterization and application, it is necessary to know their acid-base properties, particularly the acidity constants (pK a ) of their ionogenic groups (the basic N 3 atom of the triazine ring and the acidic phosphonic acid group in the alkyl chain). First, the mixed acidity constants (pK a mix ) of these ionogenic groups and the ionic mobilities of these compounds were determined by nonlinear regression analysis of the pH dependence of their effective electrophoretic mobilities. Effective mobilities were measured by CE in a series of background electrolytes in a wide pH range (2.0-10.5), at constant ionic strength (25mM) and constant temperature (25°C). Subsequently, the pK a mix values were recalculated to thermodynamic pK a values using the Debye-Hückel theory. The thermodynamic pK a value of the NH + moiety at the N 3 atom of the triazine ring was found to be in the range 2.82-3.30, whereas the pK a of the hydrogenphosphonate group reached values from 7.19 to 7.47, depending on the structure of the analyzed compounds. These experimentally determined pK a values were in good agreement with those calculated by quantum mechanical DFT. In addition, DFT calculations revealed that from the four nitrogen atoms in the 5-azacytosine moiety, the N 3 atom of the triazine ring is preferentially protonated. Effective charges of analyzed compounds ranged from zero or close-to-zero values at pH 2 to -2 elementary charges at pH≥9. Ionic mobilities were in the range (-16.7 to -19.1)×10 -9 m 2 V -1 s -1 for univalent anions and in the interval (-26.9 to -30.3)×10 -9 m 2 V -1 s -1 for divalent anions. Copyright © 2016 Elsevier B.V. All rights reserved.

Triggering the Chemical Instability of an Ionic Liquid under High Pressure.

PubMed

Faria, Luiz F O; Nobrega, Marcelo M; Temperini, Marcia L A; Bini, Roberto; Ribeiro, Mauro C C

2016-09-01

Ionic liquids are an interesting class of materials due to their distinguished properties, allowing their use in an impressive range of applications, from catalysis to hypergolic fuels. However, the reactivity triggered by the application of high pressure can give rise to a new class of materials, which is not achieved under normal conditions. Here, we report on the high-pressure chemical instability of the ionic liquid 1-allyl-3-methylimidazolium dicyanamide, [allylC1im][N(CN)2], probed by both Raman and IR techniques and supported by quantum chemical calculations. Our results show a reaction occurring above 8 GPa, involving the terminal double bond of the allyl group, giving rise to an oligomeric product. The results presented herein contribute to our understanding of the stability of ionic liquids, which is of paramount interest for engineering applications. Moreover, gaining insight into this peculiar kind of reactivity could lead to the development of new or alternative synthetic routes to achieve, for example, poly(ionic liquids).

Influence of Nanosegregation on the Surface Tension of Fluorinated Ionic Liquids

PubMed Central

Luís, Andreia; Shimizu, Karina; Araújo, João M. M.; Carvalho, Pedro J.; Lopes-da-Silva, José A.; Canongia Lopes, José N.; Rebelo, Luís Paulo N.; Coutinho, João A. P.; Freire, Mara G.; Pereiro, Ana B.

2017-01-01

We have investigated, both theoretically and experimentally, the balance between the presence of alkyl and perfluoroalkyl side chains on the surface organization and surface tension of fluorinated ionic liquids (FILs). A series of ILs composed of 1-alkyl-3-methylimidazolium cations ([CnC1im] with n = 2, 4, 6, 8, 10 or 12) combined with the perfluorobutanesulfonate anion was used. The surface tensions of the investigated liquid salts are considerably lower than those reported for non-fluorinated ionic liquids. The most surprising and striking feature was the identification, for the first time, of a minimum at n = 8 in the surface tension versus the length of the IL cation alkyl side chain. Supported by molecular dynamic simulations it was found that this trend is a result of the competition between the two nonpolar domains (perfluorinated and aliphatic) on pointing towards the gas-liquid interface, a phenomenon which occurs in ionic liquids with perfluorinated anions. Furthermore, these ionic liquids present the lowest surface entropy reported to date. PMID:27218210

Synthesis and characterization of ionomers as polymer electrolytes for energy conversion devices

NASA Astrophysics Data System (ADS)

Oh, Hyukkeun

Single-ion conducting electrolytes present a unique alternative to traditional binary salt conductors used in lithium-ion batteries. Secondary lithium batteries are considered as one of the leading candidates to replace the combustible engines in automotive technology, however several roadblocks are present which prevent their widespread commercialization. Power density, energy density and safety properties must be improved in order to enable the current secondary lithium battery technology to compete with existing energy technologies. It has been shown theoretically that single-ion electrolytes can eliminate the salt concentration gradient and polarization loss in the cell that develops in a binary salt system, resulting in substantial improvements in materials utilization for high power and energy densities. While attempts to utilize single-ion conducting electrolytes in lithium-ion battery systems have been made, the low ionic conductivities prevented the successful operation of the battery cells in ambient conditions. This work focuses on designing single-ion conducting electrolytes with high ionic conductivities and electrochemical and mechanical stability which enables the stable charge-discharge performance of battery cells. Perfluorosulfonate ionomers are known to possess exceptionally high ionic conductivities due to the electron-withdrawing effect caused by the C-F bonds which stabilizes the negative charge of the anion, leading to a large number of free mobile cations. The effect of perfluorinated sulfonic acid side chains on transport properties of proton exchange membrane polymers was examinated via a comparison of three ionomers, having different side chain structures and a similar polymer backbone. The three different side chain structures were aryl-, pefluoro alkyl-, and alkyl-sulfonic acid groups, respectively. All ionomers were synthesized and characterized by 1H and 19F NMR. A novel ionomer synthesized with a pendant perfluorinated sulfonic acid group and a poly(ether ether ketone) backbone showed the highest proton conductivity and proton diffusion coefficient among the three ionomers, demonstrating the effect of the perfluorinated side chains. The proton conductivity of the novel ionomer was comparable to that of Nafion over a wide humidity range and temperature. A lithium perfluorosulfonate ionomer based on aromatic poly(arylene ether)s with pendant lithium perfluoroethyl sulfonates was prepared by ion exchange of the perlfuorosulfonic acid ionomer, and subsequently incoroporated into a lithium-ion battery cell as a single-ion conducting electrolyte. The microporous polymer film saturated with organic carbonates exhibited a nearly unity Li + transfer number, high ionic conductivity (e.g. > 10-3 S m-1 at room temperature) over a wide range of temperatures, high electrochemical stability, and excellent mechanical properties. Excellent cyclability with almost identical charge and discharge capacities have been demonstrated at ambient temperature in the batteries assembled from the prepared single-ion conductors. The mechanical stability of the polymer film was attributed to the rigid polymer backbone which was largely unaffected by the presence of plasticizing organic solvents, while the porous channels with high concentration of the perfluorinated side chains resulted in high ionic conductivity. The expected high charge-rate performance was not achieved, however, due to the high interfacial impedance present between the polymer electrolyte and the electrodes. Several procedural modifications were employed in order to decrease the interfacial impedance of the battery cell. The poly(arylene ether) based ionomer was saturated with an ionic liquid mixture, in order to explore the possibility of its application as a safe, inflammable electrolyte. A low-viscosity ionic liquid with high ionic conductivity, 1-butyl-3-methylimidazolium thiocyanate which has never been successfully utilized as an electrolyte for lithium-ion batteries was incorporated into a battery cell as a solvent mixture with propylene carbonate and lithium bis(trifluoromethane)sulfonimide impregnated in a free-standing hybrid electrolyte film. Outstanding ionic conductivity was achieved and the lithium half cell comprising a LTO cathode and a lithium metal anode separated by the solid polymer electrolyte showed good cyclability at room temperature and even at 0°C. The presence of a sufficient amount of propylene carbonate, which resulted in flammability of the polymer electrolyte, was discovered to be critical in the electrochemical stability of the polymer electrolyte.

The Effect of Microporous Polymeric Support Modification on Surface and Gas Transport Properties of Supported Ionic Liquid Membranes

PubMed Central

Akhmetshina, Alsu A.; Davletbaeva, Ilsiya M.; Grebenschikova, Ekaterina S.; Sazanova, Tatyana S.; Petukhov, Anton N.; Atlaskin, Artem A.; Razov, Evgeny N.; Zaripov, Ilnaz I.; Martins, Carla F.; Neves, Luísa A.; Vorotyntsev, Ilya V.

2015-01-01

Microporous polymers based on anionic macroinitiator and toluene 2,4-diisocyanate were used as a support for 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([emim][Tf2N]) immobilization. The polymeric support was modified by using silica particles associated in oligomeric media, and the influence of the modifier used on the polymeric structure was studied. The supported ionic liquid membranes (SILMs) were tested for He, N2, NH3, H2S, and CO2 gas separation and ideal selectivities were calculated. The high values of ideal selectivity for ammonia-based systems with permanent gases were observed on polymer matrixes immobilized with [bmim][PF6] and [emim][Tf2N]. The modification of SILMs by nanosize silica particles leads to an increase of NH3 separation relatively to CO2 or H2S. PMID:26729177

Adsorption mechanism for xanthene dyes to cellulose granules.

PubMed

Tabara, Aya; Yamane, Chihiro; Seguchi, Masaharu

2012-01-01

The xanthene dyes, erythrosine, phloxine, and rose bengal, were adsorbed to charred cellulose granules. The charred cellulose granules were preliminarily steeped in ionic (NaOH, NaCl, KOH, KCl, and sodium dodecyl sulfate (SDS)), nonionic (glucose, sucrose, and ethanol), and amphipathic sucrose fatty acid ester (SFAE) solutions, and adsorption tests on the dye to the steeped and charred cellulose granules were conducted. Almost none of the dye was adsorbed when the solutions of ionic and amphipathic molecules were used, but were adsorbed in the case of steeping in the nonionic molecule solutions. Thin-layer chromatography (TLC) and the Fourier transform infra-red (FT-IR) profiles of SFAE which was adsorbed to the charred cellulose granules and extracted by ethyl ether suggested the presence of hydrophobic sites on the surface of the charred cellulose granules. We confirmed that the xanthene dyes could bind to the charred cellulose granules by ionic and hydrophobic bonds.

Electrochemical Supercapacitor Electrodes from Sponge-like Graphene Nanoarchitectures with Ultrahigh Power Density.

PubMed

Xu, Zhanwei; Li, Zhi; Holt, Chris M B; Tan, Xuehai; Wang, Huanlei; Amirkhiz, Babak Shalchi; Stephenson, Tyler; Mitlin, David

2012-10-18

We employed a microwave synthesis process of cobalt phthalocyanine molecules templated by acid-functionalized multiwalled carbon nanotubes to create three-dimensional sponge-like graphene nanoarchitectures suited for ionic liquid-based electrochemical capacitor electrodes that operate at very high scan rates. The sequential "bottom-up" molecular synthesis and subsequent carbonization process took less than 20 min to complete. The 3D nanoarchitectures are able to deliver an energy density of 7.1 W·h kg(-1) even at an extra high power density of 48 000 W kg(-1). In addition, the ionic liquid supercapacitor based on this material works very well at room temperature due to its fully opened structures, which is ideal for the high-power energy application requiring more tolerance to temperature variation. Moreover, the structures are stable in both ionic liquids and 1 M H2SO4, retaining 90 and 98% capacitance after 10 000 cycles, respectively.

Sulfonated Copper Phthalocyanine/Sulfonated Polysulfone Composite Membrane for Ionic Polymer Actuators with High Power Density and Fast Response Time.

PubMed

Kwon, Taehoon; Cho, Hyeongrae; Lee, Jang-Woo; Henkensmeier, Dirk; Kang, Youngjong; Koo, Chong Min

2017-08-30

Ionic polymer composite membranes based on sulfonated poly(arylene ether sulfone) (SPAES) and copper(II) phthalocyanine tetrasulfonic acid (CuPCSA) are assembled into bending ionic polymer actuators. CuPCSA is an organic filler with very high sulfonation degree (IEC = 4.5 mmol H + /g) that can be homogeneously dispersed on the molecular scale into the SPAES membrane, probably due to its good dispersibility in SPAES-containing solutions. SPAES/CuPCSA actuators exhibit larger ion conductivity (102 mS cm -1 ), tensile modulus (208 MPa), strength (101 MPa), and strain (1.21%), exceptionally faster response to electrical stimuli, and larger mechanical power density (3028 W m -3 ) than ever reported for ion-conducting polymer actuators. This outstanding actuation performance of SPAES/CuPCSA composite membrane actuators makes them attractive for next-generation transducers with high power density, which are currently developed, e.g., for underwater propulsion and endoscopic surgery.

New membranes based on ionic liquids for PEM fuel cells at elevated temperatures

NASA Astrophysics Data System (ADS)

Ye, H.; Huang, J.; Xu, J. J.; Kodiweera, N. K. A. C.; Jayakody, J. R. P.; Greenbaum, S. G.

Proton exchange membrane (PEM) fuel cells operating at elevated temperature, above 120 °C, will yield significant benefits but face big challenges for the development of suitable PEMs. The objectives of this research are to demonstrate the feasibility of the concept and realize [acid/ionic liquid/polymer] composite gel-type membranes as such PEMs. Novel membranes consisting of anhydrous proton solvent H 3PO 4, the protic ionic liquid PMIH 2PO 4, and polybenzimidazole (PBI) as a matrix have been prepared and characterized for PEM fuel cells intended for operation at elevated temperature (120-150 °C). Physical and electrochemical analyses have demonstrated promising characteristics of these H 3PO 4/PMIH 2PO 4/PBI membranes at elevated temperature. The proton transport mechanism in these new membranes has been investigated by Fourier transform infrared and nuclear magnetic resonance spectroscopic methods.

Structure and diffusion of furans and other cellulose-derived compounds in solvents via MD simulation

NASA Astrophysics Data System (ADS)

Rabideau, Brooks; Ismail, Ahmed

2011-03-01

There is now a large push towards the development of energy sources that are both environmentally friendly and sustainable; with the conversion of cellulose derived from biomass into biofuels being one promising route. In this conversion, a variety of intermediary compounds have been identified, which appear critical to successful expansion of the process to an industrial scale. Here we examine the structure and diffusion of these furans and acids derived from cellulose within ionic liquids via molecular dynamic simulation. Ionic liquids have shown the ability to dissolve cellulose with certain `green' benefits over existing, conventional solvents. Specifically, we study the solvation properties of these chemicals by examining the pair correlation functions of solute with solvent, and by exploring the agglomeration and separation of these chemicals from the solvent as well as the hydrogen bonding between species. Additionally, we determine the diffusion constant of these compounds in ionic liquid and aqueous solvents.

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.

Improved Activity of a Thermophilic Cellulase, Cel5A, from Thermotoga maritima on Ionic Liquid Pretreated Switchgrass

PubMed Central

Chen, Zhiwei; Pereira, Jose H.; Liu, Hanbin; Tran, Huu M.; Hsu, Nathan S. Y.; Dibble, Dean; Singh, Seema; Adams, Paul D.; Sapra, Rajat; Hadi, Masood Z.; Simmons, Blake A.; Sale, Kenneth L.

2013-01-01

Ionic liquid pretreatment of biomass has been shown to greatly reduce the recalcitrance of lignocellulosic biomass, resulting in improved sugar yields after enzymatic saccharification. However, even under these improved saccharification conditions the cost of enzymes still represents a significant proportion of the total cost of producing sugars and ultimately fuels from lignocellulosic biomass. Much of the high cost of enzymes is due to the low catalytic efficiency and stability of lignocellulolytic enzymes, especially cellulases, under conditions that include high temperatures and the presence of residual pretreatment chemicals, such as acids, organic solvents, bases, or ionic liquids. Improving the efficiency of the saccharification process on ionic liquid pretreated biomass will facilitate reduced enzyme loading and cost. Thermophilic cellulases have been shown to be stable and active in ionic liquids but their activity is typically at lower levels. Cel5A_Tma, a thermophilic endoglucanase from Thermotoga maritima, is highly active on cellulosic substrates and is stable in ionic liquid environments. Here, our motivation was to engineer mutants of Cel5A_Tma with higher activity on 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]) pretreated biomass. We developed a robotic platform to screen a random mutagenesis library of Cel5A_Tma. Twelve mutants with 25–42% improvement in specific activity on carboxymethyl cellulose and up to 30% improvement on ionic-liquid pretreated switchgrass were successfully isolated and characterized from a library of twenty thousand variants. Interestingly, most of the mutations in the improved variants are located distally to the active site on the protein surface and are not directly involved with substrate binding. PMID:24244549

Improved activity of a thermophilic cellulase, Cel5A, from Thermotoga maritima on ionic liquid pretreated switchgrass.

PubMed

Chen, Zhiwei; Pereira, Jose H; Liu, Hanbin; Tran, Huu M; Hsu, Nathan S Y; Dibble, Dean; Singh, Seema; Adams, Paul D; Sapra, Rajat; Hadi, Masood Z; Simmons, Blake A; Sale, Kenneth L

2013-01-01

Ionic liquid pretreatment of biomass has been shown to greatly reduce the recalcitrance of lignocellulosic biomass, resulting in improved sugar yields after enzymatic saccharification. However, even under these improved saccharification conditions the cost of enzymes still represents a significant proportion of the total cost of producing sugars and ultimately fuels from lignocellulosic biomass. Much of the high cost of enzymes is due to the low catalytic efficiency and stability of lignocellulolytic enzymes, especially cellulases, under conditions that include high temperatures and the presence of residual pretreatment chemicals, such as acids, organic solvents, bases, or ionic liquids. Improving the efficiency of the saccharification process on ionic liquid pretreated biomass will facilitate reduced enzyme loading and cost. Thermophilic cellulases have been shown to be stable and active in ionic liquids but their activity is typically at lower levels. Cel5A_Tma, a thermophilic endoglucanase from Thermotoga maritima, is highly active on cellulosic substrates and is stable in ionic liquid environments. Here, our motivation was to engineer mutants of Cel5A_Tma with higher activity on 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]) pretreated biomass. We developed a robotic platform to screen a random mutagenesis library of Cel5A_Tma. Twelve mutants with 25-42% improvement in specific activity on carboxymethyl cellulose and up to 30% improvement on ionic-liquid pretreated switchgrass were successfully isolated and characterized from a library of twenty thousand variants. Interestingly, most of the mutations in the improved variants are located distally to the active site on the protein surface and are not directly involved with substrate binding.

LEWIS ACID CATALYZED FORMATION OF TETRAHYDROPYRANS IN IONIC LIQUID

EPA Science Inventory

Tetrahydropyrans are integral moieties in innumerable natural products and have inspired the development of a variety of different methodologies. A Prins-type cyclization involving the coupling of a homoallylic alcohol and an aldehyde in the presence of catalytic scandium triflat...

DIFMOD2: A NEXT GENERATION DIFFUSE LAYER MODEL

EPA Science Inventory

Jenne (1998) suggested that the majority of uncertainty in our current ability to model the environmental partitioning behavior of ionic species on natural surfaces resulted from uncertainties in our understanding of surface acidity behavior. Traditional 2-pK Grahame-Gouy-Chapma...

Modeling the controllable pH-responsive swelling and pore size of networked alginate based biomaterials.

PubMed

Chan, Ariel W; Neufeld, Ronald J

2009-10-01

Semisynthetic network alginate polymer (SNAP), synthesized by acetalization of linear alginate with di-aldehyde, is a pH-responsive tetrafunctionally linked 3D gel network, and has potential application in oral delivery of protein therapeutics and active biologicals, and as tissue bioscaffold for regenerative medicine. A constitutive polyelectrolyte gel model based on non-Gaussian polymer elasticity, Flory-Huggins liquid lattice theory, and non-ideal Donnan membrane equilibria was derived, to describe SNAP gel swelling in dilute and ionic solutions containing uni-univalent, uni-bivalent, bi-univalent or bi-bi-valent electrolyte solutions. Flory-Huggins interaction parameters as a function of ionic strength and characteristic ratio of alginates of various molecular weights were determined experimentally to numerically predict SNAP hydrogel swelling. SNAP hydrogel swells pronouncedly to 1000 times in dilute solution, compared to its compact polymer volume, while behaving as a neutral polymer with limited swelling in high ionic strength or low pH solutions. The derived model accurately describes the pH-responsive swelling of SNAP hydrogel in acid and alkaline solutions of wide range of ionic strength. The pore sizes of the synthesized SNAP hydrogels of various crosslink densities were estimated from the derived model to be in the range of 30-450 nm which were comparable to that measured by thermoporometry, and diffusion of bovine serum albumin. The derived equilibrium swelling model can characterize hydrogel structure such as molecular weight between crosslinks and crosslinking density, or can be used as predictive model for swelling, pore size and mechanical properties if gel structural information is known, and can potentially be applied to other point-link network polyelectrolytes such as hyaluronic acid gel.

High-efficiency extracellular release of free fatty acids from Aspergillus oryzae using non-ionic surfactants.

PubMed

Tamano, Koichi; Miura, Ai; Koike, Hideaki; Kamisaka, Yasushi; Umemura, Myco; Machida, Masayuki

2017-04-20

Free fatty acids (FFAs) are useful for generating biofuel compounds and functional lipids. Microbes are increasingly exploited to produce FFAs via metabolic engineering. However, in many microorganisms, FFAs accumulate in the cytosol, and disrupting cells to extract them is energy intensive. Thus, a simple cost-effective extraction technique must be developed to remove this drawback. We found that FFAs were released from cells of the filamentous fungus Aspergillus oryzae with high efficiency when they were cultured or incubated with non-ionic surfactants such as Triton X-100. The surfactants did not reduce hyphal growth, even at 5% (w/v). When the faaA disruptant was cultured with 1% Triton X-100, more than 80% of the FFAs synthesized de novo were released. When the disruptant cells grown without surfactants were incubated for 1h in 1% Triton X-100 solution, more than 50% of the FFAs synthesized de novo were also released. Other non-ionic surfactants in the same ether series, such as Brij 58, IGEPAL CA-630, and Tergitol NP-40, elicited a similar FFA release. The dry cell weight of total hyphae decreased when grown with 1% Triton X-100. The decrement was 4.9-fold greater than the weight of the released FFAs, implying release of other intracellular compounds. Analysis of the culture supernatant showed that intracellular lactate dehydrogenase was also released, suggesting that FFAs are not released by a specific transporter. Therefore, ether-type non-ionic surfactants probably cause non-specific release of FFAs and other intracellular compounds by increasing cell membrane permeability. Copyright © 2017 Elsevier B.V. All rights reserved.

Constitutive expression of a salinity-induced wheat WRKY transcription factor enhances salinity and ionic stress tolerance in transgenic Arabidopsis thaliana

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

Qin, Yuxiang, E-mail: yuxiangqin@126.com; Tian, Yanchen; Han, Lu

Highlights: •A class II WRKY transcription factor, TaWRKY79 was isolated and characterized. •TaWRKY79 was induced by NaCl or abscisic acid. •843 bp regulatory segment was sufficient to respond to ABA or NaCl treatment. •TaWRKY79 enhanced salinity and ionic tolerance while reduced sensitivity to ABA. •TaWRKY79 increased salinity and ionic tolerance in an ABA-dependent pathway. -- Abstract: The isolation and characterization of TaWRKY79, a wheat class II WRKY transcription factor, is described. Its 1297 bp coding region includes a 987 bp long open reading frame. TaWRKY79 was induced by stressing seedlings with either NaCl or abscisic acid (ABA). When a fusionmore » between an 843 bp segment upstream of the TaWRKY79 coding sequence and GUS was introduced into Arabidopsis thaliana, GUS staining indicated that this upstream segment captured the sequence(s) required to respond to ABA or NaCl treatment. When TaWRKY79 was constitutively expressed as a transgene in A. thaliana, the transgenic plants showed an improved capacity to extend their primary root in the presence of either 100 mM NaCl, 10 mM LiCl or 2 μM ABA. The inference was that TaWRKY79 enhanced the level of tolerance to both salinity and ionic stress, while reducing the level of sensitivity to ABA. The ABA-related genes ABA1, ABA2 ABI1 and ABI5 were all up-regulated in the TaWRKY79 transgenic plants, suggesting that the transcription factor operates in an ABA-dependent pathway.« less

Atmospheric chlorinated polyfluorinated ether sulfonate and ionic perfluoroalkyl acids in 2006 to 2014 in Dalian, China.

PubMed

Liu, Wei; Qin, Hui; Li, Jingwen; Zhang, Qian; Zhang, Huanhuan; Wang, Zaoshi; He, Xin

2017-10-01

Chlorinated polyfluorinated ether sulfonate (Cl-PFESA; trade name F-53B) is an alternative product for perfluorooctane sulfonate (PFOS) used in metal plating; little is known about its levels in the environment and its risks. To our knowledge, the present study constitutes the first report of Cl-PFESA in the atmosphere. In 2006 to 2014, C8 Cl-PFESA, along with ionic perfluoroalkyl acids (PFAAs), was detected in atmospheric particulate matter in Dalian, China. Concentrations of C8 Cl-PFESA increased from 140 pg/m 3 in 2007 to 722 pg/m 3 in 2014. Levels of 11 (total) ionic PFAAs increased in 2006 to 2008 and decreased afterward, with a range of 35.7 to 860 pg/m 3 . The PFAAs in the particulate matter were dominated by perfluorocarboxylates, with perfluorooctanoate detected at the highest concentration at a mean level of 71.7 pg/m 3 , followed by perfluoroheptanoate and perfluorohexanoate. Perfluorosulfonates were detected at lower levels, with mean concentrations of PFOS, perfluorobutanesulfonate, and perfluorohexane sulfonate of 5.73, 1.64, and 1.24 pg/m 3 , respectively. Back-trajectory analysis suggested that the air mass approaching Dalian during the sampling originated from the northwest, where fluorochemical industry parks and metal plating industries are densely located. No significant correlation was observed between Cl-PFESA and the ionic PFAAs. The relatively high Cl-PFESA concentrations suggested that it possibly contributed largely to the previously reported exposure to undefined organic fluorine compounds, for which further research on emission and environmental risks is needed. Environ Toxicol Chem 2017;36:2581-2586. © 2017 SETAC. © 2017 SETAC.

Effect of environmental factors on the kinetics of insulin fibril formation: elucidation of the molecular mechanism.

PubMed

Nielsen, L; Khurana, R; Coats, A; Frokjaer, S; Brange, J; Vyas, S; Uversky, V N; Fink, A L

2001-05-22

In the search for the molecular mechanism of insulin fibrillation, the kinetics of insulin fibril formation were studied under different conditions using the fluorescent dye thioflavin T (ThT). The effect of insulin concentration, agitation, pH, ionic strength, anions, seeding, and addition of 1-anilinonaphthalene-8-sulfonic acid (ANS), urea, TMAO, sucrose, and ThT on the kinetics of fibrillation was investigated. The kinetics of the fibrillation process could be described by the lag time for formation of stable nuclei (nucleation) and the apparent rate constant for the growth of fibrils (elongation). The addition of seeds eliminated the lag phase. An increase in insulin concentration resulted in shorter lag times and faster growth of fibrils. Shorter lag times and faster growth of fibrils were seen at acidic pH versus neutral pH, whereas an increase in ionic strength resulted in shorter lag times and slower growth of fibrils. There was no clear correlation between the rate of fibril elongation and ionic strength. Agitation during fibril formation attenuated the effects of insulin concentration and ionic strength on both lag times and fibril growth. The addition of ANS increased the lag time and decreased the apparent growth rate for insulin fibril formation. The ANS-induced inhibition appears to reflect the formation of amorphous aggregates. The denaturant, urea, decreased the lag time, whereas the stabilizers, trimethylamine N-oxide dihydrate (TMAO) and sucrose, increased the lag times. The results indicated that both nucleation and fibril growth were controlled by hydrophobic and electrostatic interactions. A kinetic model, involving the association of monomeric partially folded intermediates, whose concentration is stimulated by the air-water interface, leading to formation of the critical nucleus and thence fibrils, is proposed.

Electromembrane extraction of zwitterionic compounds as acid or base: comparison of extraction behavior at acidic and basic pHs.

PubMed

Nojavan, Saeed; Pourahadi, Ahmad; Hosseiny Davarani, Saied Saeed; Morteza-Najarian, Amin; Beigzadeh Abbassi, Mojtaba

2012-10-01

This study has performed on electromembrane extraction (EME) of some zwitterionic compounds based on their acidic and basic properties. High performance liquid chromatography (HPLC) equipped with UV detection was used for determination of model compounds. Cetirizine (CTZ) and mesalazine (MS) were chosen as model compounds, and each of them was extracted from acidic (as a cation) and basic (as an anion) sample solutions, separately. 1-Octanol and 2-nitrophenyl octylether (NPOE) were used as the common supported liquid membrane (SLM) solvents. EME parameters, such as extraction time, extraction voltage and pH of donor and acceptor solutions were studied in details for cationic and anionic forms of each model compound and obtained results for two ionic forms (cationic and anionic) of each compound were compared together. Results showed that zwitterionic compounds could be extracted in both cationic and anionic forms. Moreover, it was found that the extraction of anionic form of each model compound could be done in low voltages when 1-octanol was used as the SLM solvent. Results showed that charge type was not highly effective on the extraction efficiency of model compounds whereas the position of charge within the molecule was the key parameter. In optimized conditions, enrichment factors (EF) of 27-60 that corresponded to recoveries ranging from 39 to 86% were achieved. Copyright © 2012 Elsevier B.V. All rights reserved.

Docetaxel-loaded polylactic acid-co-glycolic acid nanoparticles: formulation, physicochemical characterization and cytotoxicity studies.

PubMed

Pradhan, Roshan; Poudel, Bijay Kumar; Ramasamy, Thiruganesh; Choi, Han-Gon; Yong, Chul Soon; Kim, Jong Oh

2013-08-01

In the present study, we developed novel docetaxel (DTX)-loaded polylactic acid-co-glycolic acid (PLGA) nanoparticles (NPs) using the combination of sodium lauryl sulfate (SLS) and poloxamer 407, the anionic and non-ionic surfactants respectively for stabilization. The NPs were prepared by emulsification/solvent evaporation method. The combination of these surfactants at weight ratio of 1:0.5 was able to produce uniformly distributed small sized NPs and demonstrated the better stability of NP dispersion with high encapsulation efficiency (85.9 +/- 0.6%). The drug/polymer ratio and phase ratio were 2:10 and 1:10, respectively. The optimized formulation of DTX-loaded PLGA NPs had a particle size and polydispersity index of 104.2 +/- 1.5 nm and 0.152 +/- 0.006, respectively, which was further supported by TEM image. In vitro release study was carried out with dialysis membrane and showed 32% drug release in 192 h. When in vitro release data were fitted to Korsmeyer-Peppas model, the n value was 0.481, which suggested the drug was released by anomalous or non-Fickian diffusion. In addition, DTX-loaded PLGA NPs in 72 h, displayed approximately 75% cell viability reduction at 10 microg/ml DTX concentration, in MCF-7 cell lines, indicating sustained release from NPs. Therefore, our results demonstrated that incorporation of DTX into PLGA NPs could provide a novel effective nanocarrier for the treatment of cancer.

Organic acids and selected nitrogen species for ABLE-3

NASA Technical Reports Server (NTRS)

Talbot, Robert W.

1991-01-01

The NASA Global Tropospheric Experiment (GTE) executed airborne science missions aboard the NASA Wallops Electra (NA429) in the North American high latitude (greater than 45 deg North) atmosphere during Jul. to Aug. 1988 and Jul. to Aug. 1990. These missions were part of GTE's Atmospheric Boundary Layer Experiment (ABLE). The 1988 mission , ABLE-3A, examined the ecosystems of Alaska as a source and/or sink for important tropospheric gases and particles, and gained new information on the chemical composition of the Arctic atmosphere during the summertime. During 1990 the second high latitude mission, ABLE-3B, focused on the Hudson Bay Lowland and Labrador regions of Canada. Both of these missions provided benchmark data sets on atmosphere biosphere exchange and atmospheric chemistry over largely uninhabited regions of North America. In support of the GTE/ABLE-3A and -3B field missions, the University of New Hampshire flew instrumentation aboard the Wallops Electra research aircraft to provide measurements of the trace gases nitric (HNO3), formic (HCOOH), and acetic (CH3COOH) acid. In addition, measurements were conducted to determine the major water soluble ionic composition of the atmospheric aerosol. For ABLE-3B, groundbased measurements of the acidic trace gases were also performed from the NASA micrometerological tower situated at Schefferville, Laborador. These measurements were aimed at assessing dry deposition of acidic gases to the taiga ecosystem in the Laborador region of Canada.

Hydrolysis of Hemicellulose and Derivatives—A Review of Recent Advances in the Production of Furfural

PubMed Central

Delbecq, Frederic; Wang, Yantao; Muralidhara, Anitha; El Ouardi, Karim; Marlair, Guy; Len, Christophe

2018-01-01

Biobased production of furfural has been known for decades. Nevertheless, bioeconomy and circular economy concepts is much more recent and has motivated a regain of interest of dedicated research to improve production modes and expand potential uses. Accordingly, this review paper aims essentially at outlining recent breakthroughs obtained in the field of furfural production from sugars and polysaccharides feedstocks. The review discusses advances obtained in major production pathways recently explored splitting in the following categories: (i) non-catalytic routes like use of critical solvents or hot water pretreatment, (ii) use of various homogeneous catalysts like mineral or organic acids, metal salts or ionic liquids, (iii) feedstock dehydration making use of various solid acid catalysts; (iv) feedstock dehydration making use of supported catalysts, (v) other heterogeneous catalytic routes. The paper also briefly overviews current understanding of furfural chemical synthesis and its underpinning mechanism as well as safety issues pertaining to the substance. Eventually, some remaining research topics are put in perspective for further optimization of biobased furfural production. PMID:29868554

XPS analysis of activated carbon supported ionic liquids: Enhanced purity and reduced charging

NASA Astrophysics Data System (ADS)

Foelske-Schmitz, A.; Weingarth, D.; Kötz, R.

2011-12-01

Herein we report on XPS measurements on five different [EMIM] based ionic liquids (IL) prepared on activated carbon and aluminium supports. The anions were [TFSI], [BF4], [FAP], [B(CN)4] and [EtOSO3]. The results show that impurities such as O, Si or hydrocarbons were significantly reduced or no longer detected when preparation was performed on the high surface area carbon support. All core level spectra were fitted and for [EMIM][FAP], [EMIM][B(CN)4] and [EMIM][EtOSO3] de-convolution procedures of the C 1s lines are suggested. Comparison of the determined binding energies with published data strongly suggests that sample charging is irrelevant when preparation is performed on the activated carbon support. This observation is supposed to refer to the high capacitance of the high surface area carbon.

Crystal and molecular structure of eight organic acid-base adducts from 2-methylquinoline and different acids

NASA Astrophysics Data System (ADS)

Zhang, Jing; Jin, Shouwen; Tao, Lin; Liu, Bin; Wang, Daqi

2014-08-01

Eight supramolecular complexes with 2-methylquinoline and acidic components as 4-aminobenzoic acid, 2-aminobenzoic acid, salicylic acid, 5-chlorosalicylic acid, 3,5-dinitrosalicylic acid, malic acid, sebacic acid, and 1,5-naphthalenedisulfonic acid were synthesized and characterized by X-ray crystallography, IR, mp, and elemental analysis. All of the complexes are organic salts except compound 2. All supramolecular architectures of 1-8 involve extensive classical hydrogen bonds as well as other noncovalent interactions. The results presented herein indicate that the strength and directionality of the classical hydrogen bonds (ionic or neutral) between acidic components and 2-methylquinoline are sufficient to bring about the formation of binary organic acid-base adducts. The role of weak and strong noncovalent interactions in the crystal packing is ascertained. These weak interactions combined, the complexes 1-8 displayed 2D-3D framework structure.

Computational modeling of the structure and the ionic conductivity of the solid electrolyte materials Li3AsS4 and its Ge substitutions

NASA Astrophysics Data System (ADS)

Al-Qawasmeh, Ahmad; Holzwarth, N. A. W.

Oak Ridge National Laboratory (G. Sahu et al.) reported that the substitution of Ge into Li3AsS4 leads to the composition Li3.334Ge0.334As0.666S4 with impressively high ionic conductivity . We use ab initio calculations to examine the structural relationships and the ionic conductivity mechanisms for pure Li3AsS4, Li3.334Ge0.334As0.666S4, and other compositions of these electrolytes. Supported by NSF Grant DMR-1105485 and 1507942 and WFU's DEAC cluster.

New Pyrazolium Salts as a Support for Ionic Liquid Crystals and Ionic Conductors.

PubMed

Pastor, María Jesús; Sánchez, Ignacio; Campo, José A; Schmidt, Rainer; Cano, Mercedes

2018-04-03

Ionic liquid crystals (ILCs) are a class of materials that combine the properties of liquid crystals (LCs) and ionic liquids (ILs). This type of materials is directed towards properties such as conductivity in ordered systems at different temperatures. In this work, we synthesize five new families of ILCs containing symmetrical and unsymmetrical substituted pyrazolium cations, with different alkyl long-chains, and anions such as Cl - , BF₄ - , ReO₄ - , p -CH₃-₆H₄SO₃ - (PTS) and CF₃SO₃ - (OTf). We study their thermal behavior by polarized light optical microscopy (POM) and differential scanning calorimetry (DSC). All of them, except those with OTf as counteranion, show thermotropic mesomorphism. The observations by POM reveal textures of lamellar mesophases. Those agree with the arrangement observed in the X-ray crystal structure of [H₂pz R(4),R(4) ][ReO₄]. The nature of the mesophases is also confirmed by variable temperature powder X-ray diffraction. On the other hand, the study of the dielectric properties at variable temperature in mesomorphic (Cl - and BF₄ - ) and non-mesomorphic (OTf) salts indicates that the supramolecular arrangement of the mesophase favors a greater ionic mobility and therefore ionic conductivity.

[Impact of acid mining drainage on the quality of superficial waters and sediments in the Marrakesh region, Morocco].

PubMed

El Gharmali, A; Rada, A; El Adnani, M; Tahlil, N; El Meray, M; Nejmeddine, A

2004-12-01

The aim of the present study is the evaluation of the effects of the acid drainage of three abandoned mining sites: SB-Othmane, Kettara and Draâ-sfar, on water and sediment quality of the Tensift River and its two temporary tributaries, the Kettara and El-Coudia Oueds. These mining sites located near Marrakesh contain mining residues abandoned for ten to twenty years. They are presently in an agricultural region of the Haouz district. In each site, these uncontrolled mining residues present a high level of metallic sulphide and generate, during rainy periods, leaching products which have physical and chemical characteristics of acid mine drainage (AMD). These percolates display an acidic pH ranging from 2.5 to 5.2, a high electric conductivity, large amounts of sulphate and heavy metals, especially under dissolved form (e.g. Cd: 17.34 mg l(-1); Fe: 1734 mg l(-1); Zn: 3935 mg l(-1)). Except for Pb, the free ionic form is the most abundant metallic form, as showed by calculations using the speciation GEOCHEM program. The analysis of water and sediments of the surrounding superficial aquatic ecosystems shows a modification of water chemical facies and an enrichment in heavy metals, mainly under the solid phase for Fe, Pb, Cu, Co, Cr and Ni, and under dissolved fraction for Cd and Zn. The dissolved fraction of these metals is dominated by the free ionic form, considered as available for organisms. Furthermore, sediments contain important quantities of heavy metals (Pb: 1450 microg g(-1), Zn: 1562 microg g(-1)) with an available fraction which is higher than 40% for the Cd and Zn. The abundance of trace elements (free ionic and available forms) in water and sediment presents a durable risk of their transfer to food chains.

THE KINETICS OF SAPONIFICATION OF IODOACETIC ACID BY SODIUM HYDROXIDE AND BY CERTAIN ALKALINE BUFFER SOLUTIONS.

PubMed

Brdicka, R

1936-07-20

1. The rate of the saponification of iodoacetic acid in sodium hydroxide and alkaline buffer solutions yielding glycollic acid was measured by means of Heyrovský's polarographic method. 2. From the bimolecular velocity constants, increasing with the ionic strength of the solution, the Brönsted factor, F, which characterizes the primary salt effect, was calculated. 3. In the borate buffer solutions the monomolecular constants of the saponification were determined which, at values above the pH of neutralization of boric acid, show a proportionality to the concentration of hydroxyl anions. Below the pH of neutralization of boric acid, they are proportional to the concentration of borate anions.

Continuous-flow hydrogenation of carbon dioxide to pure formic acid using an integrated scCO2 process with immobilized catalyst and base.

PubMed

Wesselbaum, Sebastian; Hintermair, Ulrich; Leitner, Walter

2012-08-20

Dual role for CO(2): Pure formic acid can be obtained continuously by hydrogenation of CO(2) in a single processing unit. An immobilized ruthenium organometallic catalyst and a nonvolatile base in an ionic liquid (IL) are combined with supercritical CO(2) as both reactant and extractive phase. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Computational study on nitronium and nitrosonium oxalate: potential oxidizers for solid rocket propulsion?

PubMed

Gökçinar, Elif; Klapötke, Thomas M; Kramer, Michael P

2010-08-26

The enthalpies of formation for solid ionic nitrosonium oxalate, [NO](2)[O(2)C-CO(2)], nitronium oxalate, [NO(2)](2)[O(2)C-CO(2)], as well as covalent bis(nitroso)oxalic acid, ON-O(2)C-CO(2)-NO, and oxalic acid dinitrate ester, O(2)N-O(2)C-CO(2)-NO(2), were calculated using the complete basis set (CBS-4M) method of Petersson and coworkers to obtain very accurate energies. For the nitrosonium species, the ionic form ([NO](2)[O(2)C-CO(2)]) was identified as the more stable isomer, whereas for the nitrosonium compound, the covalently bound dinitrate ester (O(2)N-O(2)C-CO(2)-NO(2)) was found to be more stable. The combustion parameters with respect to possible use as ingredients in solid rocket motors for both stable species were calculated using the EXPLO5 and the ICT code. The performance of an aluminized formulation with covalently bound dinitrate ester (O(2)N-O(2)C-CO(2)-NO(2)) was shown to be comparable to that of ammonium perchlorate/aluminum. This makes oxalic acid dinitrate ester a potentially interesting perchlorate-free and environmentally benign oxidizer for solid rocket propulsion.

The enhancement of the hydrolysis of bamboo biomass in ionic liquid with chitosan-based solid acid catalysts immobilized with metal ions.

PubMed

Cheng, Jie; Wang, Nan; Zhao, Dezhou; Qin, Dandan; Si, Wenqing; Tan, Yunfei; Wei, Shun'an; Wang, Dan

2016-11-01

Three kinds of sulfonated cross-linked chitosan (SCCR) immobilized with metal ions of Cu(2+), Fe(3+) and Zn(2+) individually were synthesized and firstly used as solid acid catalysts in the hydrolysis of bamboo biomass. FTIR spectra showed that metal ions had been introduced into SCCR and the N-metal ions coordinate bound was formed. The particle sizes of these catalysts were about 500-1000μm with a pore size of 50-160μm. All of the three kinds of catalysts performed well for bamboo hydrolysis with 1-butyl-3-methyl-imidazolium chloride used as solvent. The most effective one was sulfonated cross-linked chitosan immobilized with Fe(3+) (Fe(3+)-SCCR). TRS yields were up to 73.42% for hydrolysis of bamboo powder in [C4mim]Cl with Fe(3+)-SCCR at 120°C and 20RPM after 24h. These novel chitosan-based metal ions immobilized solid acid catalysts with ionic liquids as the solvent might be promising to facilitate cost-efficient conversion of biomass into biofuels and bioproducts. Copyright © 2016 Elsevier Ltd. All rights reserved.

Enhanced Electro-Static Modulation of Ionic Diffusion through Carbon Nanotube Membranes by Diazonium Grafting Chemistry

PubMed Central

Majumder, Mainak; Keis, Karin; Zhan, Xin; Meadows, Corey; Cole, Jeggan

2013-01-01

A membrane structure consisting of an aligned array of open ended carbon nanotubes (~ 7 nm i.d.) spanning across an inert polymer matrix allows the diffusive transport of aqueous ionic species through CNT cores. The plasma oxidation process that opens CNTs tips inherently introduces carboxylic acid groups at the CNT tips, which allows for a limited amount of chemical functional at the CNT pore entrance. However for numerous applications, it is important to increase the density of carboxylic acid groups at the pore entrance for effective separation processes. Aqueous diazonium based electro-chemistry significantly increases the functional density of carboxylic acid groups. pH dependent dye adsorption-desorption and interfacial capacitance measurements indicate ~ 5–6 times increase in functional density. To further control the spatial location of the functional chemistry, a fast flowing inert liquid column inside the CNT core is found to restrict the diazonium grafting to the CNT tips only. This is confirmed by the increased flux of positively charged Ru(bi-py)3+2 with anionic functionality. The electrostatic enhancement of ion diffusion is readily screened in 0.1(M) electrolyte solution consistent with the membrane pore geometry and increased functional density. PMID:25132719

Separation of toxic rhodamine B from aqueous solution using an efficient low-cost material, Azolla pinnata, by adsorption method.

PubMed

Kooh, Muhammad Raziq Rahimi; Lim, Linda B L; Lim, Lee Hoon; Dahri, Muhammad Khairud

2016-02-01

This study investigated the potential of untreated Azolla pinnata (AP) to remove toxic rhodamine B (RB) dye. The effects of adsorbent dosage, pH, ionic strength, contact time, and concentration were studied. Experiments involving the effects of pH and ionic strength indicated that hydrophobic-hydrophobic interactions might be the dominant force of attraction for the RB-AP adsorption system. The kinetics modelling of the kinetics experiment showed that pseudo-second-order best represented the adsorption process. The Weber-Morris intraparticle diffusion model showed that intraparticle diffusion is not the rate-limiting step, while the Boyd model suggested that film diffusion might be rate-limiting. The adsorption isotherm model, Langmuir, best represented the adsorption process, and the maximum adsorption capacity was predicted to be 72.2 and 199.7 mg g(-1) at 25 and 65 °C, respectively. Thermodynamics study indicates spontaneity, endothermic and physisorption-dominant adsorption process. The adsorbents were regenerated to satisfactory level with distilled water, HNO3 and NaOH. Pre-treatment of adsorbent with oxalic acid, citric acid, NaOH, HCl and phosphoric acid was investigated but the adsorption capacity was less than the untreated AP.

Evaluation of Toxicity and Biodegradability of Cholinium Amino Acids Ionic Liquids

PubMed Central

Hou, Xue-Dan; Liu, Qiu-Ping; Smith, Thomas J.; Li, Ning; Zong, Min-Hua

2013-01-01

Cholinium amino acid ionic liquids ([Ch][AA] ILs), which are wholly composed of renewable biomaterials, have recently been demonstrated to have very promising properties for applications in organic synthesis and biomass pretreatment. In this work, the toxicity of these ILs toward enzymes and bacteria was assessed, and the effect of the anion on these properties is discussed. The inhibitory potentials of this type of ILs to acetylcholinesterase were weaker approximately an order of magnitude than the traditional IL 1-butyl-3-methylimidazolium tetrafluoroborate. Additionally, the [Ch][AA] ILs displayed low toxicity toward the bacteria tested. Furthermore, the biodegradability of the [Ch][AA] ILs was evaluated via the closed bottle and CO2 headspace tests using wastewater microorganisms. All the ILs were classified as ‘readily biodegradable’ based on their high levels of mineralization (62-87%). The presence of extra carboxyl or amide groups on the amino acid side chain rendered the ILs significantly more susceptible to microbial breakdown. In addition, for most of the [Ch][AA] ILs, low toxicity correlated with good biodegradability. The low toxicity and high biodegradability of these novel [Ch][AA] make them promising candidates for use as environmentally friendly solvents in large-scale applications. PMID:23554985

Enrofloxacin sorption on smectite clays: effects of pH, cations, and humic acid.

PubMed

Yan, Wei; Hu, Shan; Jing, Chuanyong

2012-04-15

Enrofloxacin (ENR) occurs widely in natural waters because of its extensive use as a veterinary chemotherapeutic agent. To improve our understanding of the interaction of this emerging contaminant with soils and sediments, sorption of ENR on homoionic smectites and kaolinite was studied as a function of pH, ionic strength, exchangeable cations, and humic acid concentration. Batch experiments and in situ ATR-FTIR analysis suggested multiple sorption mechanisms. Cation exchange was a major contributor to the sorption of cationic ENR species on smectite. The decreased ENR sorption with increasing ionic strength indicated the formation of outer-sphere complexes. Exchangeable cations significantly influenced the sorption capacity, and the observed order was Cs

Glial diffusion barriers during aging and pathological states.

PubMed

Syková, E

2001-01-01

In conclusion, glial cells control not only ECS ionic composition, but also ECS size and geometry. Since ECS ionic and volume changes have been shown to play an important role in modulating the complex synaptic and extrasynaptic signal transmission in the CNS, glial cells may thus affect neuronal interaction, synchronization and neuron-glia communication. As shown in Fig. 2, a link between ionic and volume changes and signal transmission has been proposed as a model for the non-specific feedback mechanism suppressing neuronal activity (Syková, 1997; Ransom, 2000). First, neuronal activity results in the accumulation of [K+]e, which in turn depolarizes glial cells, and this depolarization induces an alkaline shift in glial pHi. Second, the glial cells extrude acid and the resulting acid shift causes a decrease in the neuronal excitability. Because ionic transmembrane shifts are always accompanied by water, this feedback mechanism is amplified by activity-related glial swelling compensated for by ECS volume shrinkage and by increased tortuosity, presumably by the crowding of molecules of the ECS matrix and/or by the swelling of fine glial processes. This, in turn, results in a larger accumulation of ions and other neuroactive substances in the brain due to increased diffusion hinderance in the ECS. Astrocyte hypertrophy, proliferation and swelling influence the size of the ECS volume and tortuosity around neurons, slowing diffusion in the ECS. Their organization may also affect diffusion anisotropy, which could be an underlying mechanism for the specificity of extrasynaptic transmission, including 'cross-talk' between distinct synapses (Barbour and Hausser, 1997; Kullmann and Asztely, 1998). An increased concentration of transmitter released into a synapse (e.g. repetitive adequate stimuli or during high frequency electrical stimulation which induces LTP) results in a significant activation of high-affinity receptors at neighboring synapses. The efficacy of such synaptic cross-talk would be dependent on the extracellular space surrounding the synapses, i.e. on intersynaptic geometry and diffusion parameters. Other recent studies have also suggested an important role for proteoglycans, known to participate in multiple cellular processes, such as axonal outgrowth, axonal branching and synaptogenesis (Hardington and Fosang, 1992; Margolis and Margolis, 1993) that are important for the formation of memory traces. Recent observation of a decrease of fibronectin and chondroitin sulfate proteoglycan staining in the hippocampus of behaviorally impaired aged rats (Syková et al., 1998a,b) supports this hypothesis. It is reasonable to assume that besides neuronal and glial processes, macromolecules of the extracellular matrix contribute to diffusion barriers in the ECS. It is therefore apparent that glial cells play an important role in the local architecture of the CNS and they may also be involved in the modulation of signal transmission, in plastic changes, LTP, LTD and in changes of behavior and memory formation.

Leaching behavior of copper from waste printed circuit boards with Brønsted acidic ionic liquid

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

Huang, Jinxiu; Chen, Mengjun, E-mail: kyling@swust.edu.cn; Chen, Haiyan

2014-02-15

Highlights: • A Brønsted acidic ILs was used to leach Cu from WPCBs for the first time. • The particle size of WPCBs has significant influence on Cu leaching rate. • Cu leaching rate was higher than 99% under the optimum leaching conditions. • The leaching process can be modeled with shrinking core model, and the E{sub a} was 25.36 kJ/mol. - Abstract: In this work, a Brønsted acidic ionic liquid, 1-butyl-3-methyl-imidazolium hydrogen sulfate ([bmim]HSO{sub 4}), was used to leach copper from waste printed circuit boards (WPCBs, mounted with electronic components) for the first time, and the leaching behavior ofmore » copper was discussed in detail. The results showed that after the pre-treatment, the metal distributions were different with the particle size: Cu, Zn and Al increased with the increasing particle size; while Ni, Sn and Pb were in the contrary. And the particle size has significant influence on copper leaching rate. Copper leaching rate was higher than 99%, almost 100%, when 1 g WPCBs powder was leached under the optimum conditions: particle size of 0.1–0.25 mm, 25 mL 80% (v/v) ionic liquid, 10 mL 30% hydrogen peroxide, solid/liquid ratio of 1/25, 70 °C and 2 h. Copper leaching by [bmim]HSO{sub 4} can be modeled with the shrinking core model, controlled by diffusion through a solid product layer, and the kinetic apparent activation energy has been calculated to be 25.36 kJ/mol.« less

Carbon-, sulfur-, and phosphorus-based charge transfer reactions in inductively coupled plasma-atomic emission spectrometry

NASA Astrophysics Data System (ADS)

Grindlay, Guillermo; Gras, Luis; Mora, Juan; de Loos-Vollebregt, Margaretha T. C.

2016-01-01

In this work, the influence of carbon-, sulfur-, and phosphorus-based charge transfer reactions on the emission signal of 34 elements (Ag, Al, As, Au, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, Ga, Hg, I, In, Ir, K, Li, Mg, Mn, Na, Ni, P, Pb, Pd, Pt, S, Sb, Se, Sr, Te, and Zn) in axially viewed inductively coupled plasma-atomic emission spectrometry has been investigated. To this end, atomic and ionic emission signals for diluted glycerol, sulfuric acid, and phosphoric acid solutions were registered and results were compared to those obtained for a 1% w w- 1 nitric acid solution. Experimental results show that the emission intensities of As, Se, and Te atomic lines are enhanced by charge transfer from carbon, sulfur, and phosphorus ions. Iodine and P atomic emission is enhanced by carbon- and sulfur-based charge transfer whereas the Hg atomic emission signal is enhanced only by carbon. Though signal enhancement due to charge transfer reactions is also expected for ionic emission lines of the above-mentioned elements, no experimental evidence has been found with the exception of Hg ionic lines operating carbon solutions. The effect of carbon, sulfur, and phosphorus charge transfer reactions on atomic emission depends on (i) wavelength characteristics. In general, signal enhancement is more pronounced for electronic transitions involving the highest upper energy levels; (ii) plasma experimental conditions. The use of robust conditions (i.e. high r.f. power and lower nebulizer gas flow rates) improves carbon, sulfur, and phosphorus ionization in the plasma and, hence, signal enhancement; and (iii) the presence of other concomitants (e.g. K or Ca). Easily ionizable elements reduce ionization in the plasma and consequently reduce signal enhancement due to charge transfer reactions.

Effect of Surfactants on Mechanical, Thermal, and Photostability of a Monoclonal Antibody.

PubMed

Agarkhed, Meera; O'Dell, Courtney; Hsieh, Ming-Ching; Zhang, Jingming; Goldstein, Joel; Srivastava, Arvind

2018-01-01

The purpose of this work was to evaluate the effect of commonly used surfactants (at 0.01% w/v concentration) on mechanical, thermal, and photostability of a monoclonal antibody (MAb1) of IgG1 sub-class and to evaluate the minimum concentration of surfactant (Polysorbate 80) required in protecting MAb1 from mechanical stress. Surfactants evaluated were non-ionic surfactants, Polysorbate 80, Polysorbate 20, Pluronic F-68 (polyoxyethylene-polyoxypropylene block polymer), Brij 35 (polyoxyethylene lauryl ether), Triton X-100, and an anionic surfactant, Caprylic acid (1-Heptanecarboxylic acid). After evaluating effect of surfactants and determining stabilizing effect of Polysorbate 80 against mechanical stress without compromising thermal and photostability of MAb1, the minimum concentration of Polysorbate 80 required for mechanical stability was further examined. Polysorbate 80 concentration was varied from 0 to 0.02%. Mechanical stability was evaluated by agitation of MAb1 at 300 rotations per minute at room temperature for 72 h. Samples were analyzed for purity by SEC-HPLC, turbidity by absorbance at 350 nm, visible particles by visual inspection, and sub-visible particles by light obscuration technique on a particle analyzer. All non-ionic surfactants tested showed a similar effect in protecting against mechanical stress and did not exhibit any significant negative effect on thermal and photostability. However, Caprylic acid had a slightly negative effect on mechanical and photostability when compared to the non-ionic surfactants or sample without surfactant. This work demonstrated that polysorbate 80 is better than other surfactants tested and that a concentration of at least 0.005% (w/v) Polysorbate 80 is needed to protect MAb1 against mechanical stress.

Sorption of Th (IV) to silica as a function of pH, humic/fulvic acid, ionic strength, electrolyte type.

PubMed

Chen, Changlun; Wang, Xiangke

2007-02-01

The removal behavior of thorium (Th(IV)) has been investigated in multicomponent systems containing silica (SiO2) as the model of inorganic particles because of its widespread presence in the earth's crust and soil humic acid (HA)/fulvic acid (FA) by batch experiments. The influence of pH from 2 to 12, ionic strength from 0.02 to 0.2 M KNO3, soil HA/FA concentration from 8.3 to 22.5 mg/L, and foreign cations (Li+, Na+, K+) and anions (NO3(-), Cl-) on the sorption of Th(IV) onto SiO2 was also tested. The sorption isotherms of Th(IV) at approximately constant pH (3.50+/-0.02) were determined and analyzed regressively with three kinds of sorption isotherm models, i.e., linear, Langmuir, and Freundlich models. The results demonstrated that the sorption of Th(IV) onto SiO2 increased steeply with increasing pH from 2 to 4. Generally, humic substances (HSs) were shown to enhance Th(IV) sorption at low pH, but to reduce Th(IV) sorption at intermediate and high pH. It was a hypothesis that the significantly positive influence of HA/FA at pH from 2 to 4 on the sorption of Th(IV) onto SiO2 was attributed to strong surface binding of HA/FA on SiO2 and subsequently the formation of ternary surface complexes such as [triple bond]MO-O-HA-Th or [triple bond]MO-O-FA-Th. The results also demonstrated that the sorption was strongly dependent on the concentration of HA/FA, and independent of ionic strength and foreign ions under our experimental conditions.

Atmospheric inputs to watersheds of the Luquillo Mountains in eastern Puerto Rico: Chapter D in Water quality and landscape processes of four watersheds in eastern Puerto Rico

USGS Publications Warehouse

Stallard, Robert F.; Murphy, Sheila F.; Stallard, Robert F.

2012-01-01

Twenty years of precipitation-chemistry data from the National Atmospheric Deposition Program site at El Verde, Puerto Rico, demonstrate that three major sources control the composition of solutes in rain in eastern Puerto Rico. In order of importance, these sources are marine salts, temperate contamination from the Northern Hemisphere, and Sahara Desert dust. Marine salts are a source of roughly 82 percent of the ionic charge in precipitation; marine salt inputs are greatest in January. Evaluation of 15 years of U.S. Geological Survey data for four watersheds in eastern Puerto Rico suggests that large storms, including hurricanes, are associated with exceptionally high chloride concentrations in stream waters. Some of these storms were missed in sampling by the National Atmospheric Deposition Program, and therefore its data on the marine contribution likely underestimate chloride. The marine contribution is a weak source of acidity. Temperate contamination contributes about 10 percent of the ionic charge in precipitation; contaminants are primarily nitrate, ammonia, and sulfate derived from various manmade and natural sources. Peak deposition of temperate contaminants is during January, April, and May, months in which strong weather fronts arrive from the north. Temperate contamination, a strong source of acidity, is the only component that is increasing through time. Sahara Desert dust provides 5 percent of the ionic charge in precipitation; it is strongly seasonal, peaking in June and July during times of maximum dust transport from the Sahara and sub-Saharan regions. This dust contributes, on average, enough alkalinity to neutralize the acidity in June and July rains.

Influence of ionic strength, anions, cations, and natural organic matter on the adsorption of pharmaceuticals to silica.

PubMed

Bui, Tung Xuan; Choi, Heechul

2010-08-01

The adsorption of four wide-use pharmaceuticals (carbamazepine, diclofenac, ibuprofen, and ketoprofen) onto a porous silica was investigated under varied ionic strengths, different anions, divalent cations (Ca(2+) and Mg(2+)), trivalent cations (Al(3+) and Fe(3+)), and natural organic matter (NOM). The experiments demonstrated that at a given pH the adsorption was most affected by ionic strength, trivalent cations, and properties of pharmaceuticals. The increase of ionic strength resulted in an increase in the adsorption of ketoprofen, but a decrease in the adsorption of carbamazepine. Trivalent metal cations made intense increases in the adsorption of three acidic pharmaceuticals, which could be due to the formation of inner-sphere complex of the cations on the surface and/or complexation of the pharmaceuticals with both surface and aqueous metal species. It was found that the adsorption of carbamazepine was not affected by divalent and trivalent cations, whereas the adsorption of diclofenac was solely impacted by the presence of Al(3+). Moreover, divalent cations at low concentration could slightly enhance the adsorption of ibuprofen and ketoprofen, whereas NOM caused a reduction in the adsorption of the tested pharmaceuticals except for diclofenac. These results suggest that ionic strength, divalent cations, trivalent cations, and NOM are notable factors affecting the adsorption of pharmaceuticals and thus the ultimate fate of pharmaceuticals in the aqueous environment. Copyright 2010 Elsevier Ltd. All rights reserved.

Search of non-ionic surfactants suitable for micellar liquid chromatography.

PubMed

Peris-García, Ester; Rodríguez-Martínez, Jorge; Baeza-Baeza, Juan J; García-Alvarez-Coque, María Celia; Ruiz-Angel, María José

2018-06-19

Most reports in reversed-phase liquid chromatography (RPLC) with micellar mobile phases make use of the anionic sodium dodecyl sulfate. This surfactant masks efficiently the silanol groups that are the origin of the poor efficiencies and tailing peaks observed for basic compounds in conventional RPLC. However, it has the handicap of yielding excessive retention, which forces the addition of an organic solvent to reduce the retention times to practical values. Other surfactants, such as the non-ionic polyoxyethylene(23)lauryl ether (Brij-35), are rarely used. Brij-35 allows the separation of a large range of analytes in adequate retention times, without the need of adding an organic solvent to the mobile phase. However, this non-ionic surfactant shows irreversible adsorption on chromatographic columns and peak shape is poorer. Therefore, the search of non-ionic surfactants with similar properties to Brij-35, but showing reversible adsorption and better peak shape, can be of great interest. In this work, the adequacy of several non-ionic surfactants as modifiers in RPLC has been explored, being polyoxyethylene(10)tridecyl ether particularly attractive. The separation of different types of compounds was checked: sulfonamides (acidic), β-adrenoceptor antagonists and tricyclic antidepressants (basic with diverse polarity), and flavonoids (with and without hydroxyl groups on the aromatic rings). The chromatographic behaviors were examined in terms of retention and peak shape. The results were compared with those obtained with Brij-35.