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Sample records for 1-butyl-3-methylimidazolium thiocyanate bmimscn

  1. Characterization of cellulose II nanoparticles regenerated from ionic liquid, 1-butyl-3-methylimidazolium chloride

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Regenerated cellulose nanoparticles (RCNs) including both elongated fiber and spherical structures were prepared from microcrystalline cellulose (MCC)and cotton using 1-butyl-3-methylimidazolium chloride followed by high-pressure homogenization. The crystalline structure of RCNs was cellulose II in ...

  2. MICROWAVE-ASSISTED PREPARATION OF 1-BUTYL-3-METHYLIMIDAZOLIUM TETRACHLOROGALLATE AND ITS CATALYTIC USE IN ACETAL FORMATION UNDER MILD CONDITIONS

    EPA Science Inventory

    1-Butyl-3-methylimidazolium tetrachlorogallate, [bmim][GaCl4], prepared via microwave-assisted protocol, is found to be an active catalyst for the efficient acetalization of aldehydes under mild conditions.

  3. Efficient production and separation of biodegradable surfactants from cellulose in 1-butyl-3-methylimidazolium chloride.

    PubMed

    Puga, Alberto V; Corma, Avelino

    2014-12-01

    Alkyl glycoside biodegradable surfactants were produced from cellulose and 1-octanol or 1-dodecanol in a one-pot, two-step (hydrolysis-glycosidation) process in 1-butyl-3-methylimidazolium chloride. Both surfactant productivity and separation efficiencies have been strikingly enhanced compared to other previously reported ionic liquid processes. Production temperatures were decreased to limit the extent of glucose dehydration and further degradation processes, but the conversions remained high. Surfactant molar yields up to 72% were achieved by operating at 70 °C. Several separation procedures were tested to achieve high recoveries of both surfactant and ionic liquid. The use of a silica stationary phase was useful for isolation of the surfactant, whereas crystallization of the ionic liquid improved its separation efficiency. Finally, the precipitation of dodecyl glycosides in aqueous media was highly efficient for their isolation and for the recovery (>99%) of the ionic liquid by using only water as the solvent for separation.

  4. Electron density analysis of 1-butyl-3-methylimidazolium chloride ionic liquid.

    PubMed

    del Olmo, Lourdes; Morera-Boado, Cercis; López, Rafael; García de la Vega, José M

    2014-06-01

    An analysis of the electron density of different conformers of the 1-butyl-3-methylimidazolium chloride (bmimCl) ionic liquid by using DFT through the BVP86 density functional has been obtained within the framework of Bader's atom in molecules (AIM), localized orbital locator (LOL), natural bond orbital (NBO), and deformed atoms in molecules (DAM). We also present an analysis of the reduced density gradients that deliver the non-covalent interaction regions and allow to understand the nature of intermolecular interactions. The most polar conformer can be characterized as ionic by AIM, LOL, and DAM methods while the most stable and the least polar shows shared-type interactions. The NBO method allows to comprehend what causes the stabilization of the most stable conformer based on analysis of the second-order perturbative energy and the charge transferred among the natural orbitals involved in the interaction. PMID:24878801

  5. Electron density analysis of 1-butyl-3-methylimidazolium chloride ionic liquid.

    PubMed

    del Olmo, Lourdes; Morera-Boado, Cercis; López, Rafael; García de la Vega, José M

    2014-06-01

    An analysis of the electron density of different conformers of the 1-butyl-3-methylimidazolium chloride (bmimCl) ionic liquid by using DFT through the BVP86 density functional has been obtained within the framework of Bader's atom in molecules (AIM), localized orbital locator (LOL), natural bond orbital (NBO), and deformed atoms in molecules (DAM). We also present an analysis of the reduced density gradients that deliver the non-covalent interaction regions and allow to understand the nature of intermolecular interactions. The most polar conformer can be characterized as ionic by AIM, LOL, and DAM methods while the most stable and the least polar shows shared-type interactions. The NBO method allows to comprehend what causes the stabilization of the most stable conformer based on analysis of the second-order perturbative energy and the charge transferred among the natural orbitals involved in the interaction.

  6. Green polymer electrolytes based on chitosan and 1-butyl-3-methylimidazolium acetate

    SciTech Connect

    Shamsudin, Intan Juliana; Ahmad, Azizan; Hassan, Nur Hasyareeda

    2014-09-03

    Green polymer electrolytes based on chitosan as the polymer matrix and ionic liquid 1-butyl-3-methylimidazolium acetate [Bmim][OAc] as charge carriers were prepared by solution casting technique. Complexes with various amount of ionic liquid loading were investigated as possible ionic conducting polymers. The ionic conductivity was found to increase with increasing weight percent of ionic liquid. The highest ionic conductivity of the charged chitosan-[Bmim][OAc] was 2.44 × 10{sup −3} S cm{sup −1} at 90 wt.% of [Bmim][OAc] content at ambient temperature. Attenuated Total Reflection Fourier Transform infrared (ATR-FTIR) spectroscopy has proven the interaction between chitosan and [Bmim][OAc]. X-ray Diffraction (XRD) has shown that the amorphosity of the complexes increase as the amount of [Bmim][OAc] increase.

  7. Electrodeposition of Nanocrystalline Chromium Coatings Based on 1-Butyl-3-Methylimidazolium-Bromide Ionic Liquid.

    PubMed

    He, Xinkuai; Zhu, Qingyun; Hou, Bailong; Cai, Youxing; Li, Chen; Fu, Liqin; Wu, Luye

    2015-12-01

    The electrochemical behavior of trivalent chromium reduction from 1-butyl-3-methylimidazolium-bromide ([BMIM]Br) ionic liquid is studied. The result of cyclic voltammetry shows that the Cr(III) reduction is irreversible and occurs in two steps, Cr(III)to Cr(II), and Cr(II) to Cr(0), respectively. In the electrochemical impedance spectroscopy measurements, the preferable equivalent circuit is made to fit the experimental data. The effects of electroplating parameters on coating thickness and electrodepositon rate are investigated by potentiostatic method on Cu electrode from Cr(III)-[BMIM]Br solution. The results show that the temperature and depositing potential have great effect on the coating thickness and electrodeposition rate. The surface morphology and composition of deposited Cr are investigated using scanning electron microscope (SEM) and energy-dispersive spectroscopy (EDS). SEM analysis shows that chromium electrodeposits obtained on Cu electrodes present a ball-like structure. EDS analysis shows that the coatings are composed of Cr. Moreover, the corrosion resistance of the as-deposited chromium layer is evaluated using polarization curves. The results show that the corrosion resistance of the chromium coatings obtained at higher potential is better.

  8. Understanding the dissolution of cellulose in 1-butyl-3-methylimidazolium acetate+DMAc solvent.

    PubMed

    Xu, Airong; Guo, Xin; Xu, Rui

    2015-11-01

    Cellulose solvent ([C4mim][CH3COO]/DMAc) could be obtained by adding N,N-dimethylacetamide (DMAc) in 1-butyl-3-methylimidazolium acetate ([C4mim][CH3COO]). The solubilities of cellulose in [C4mim][CH3COO]/DMAc solvents were determined at 25°C. The effects of molar ratio of DMAc to [C4mim][CH3COO] on cellulose solubility and the possible dissolution mechanism of cellulose in [C4mim][CH3COO]/DMAc solvent have been studied. Moreover, the regenerated cellulose from [C4mim][CH3COO]/DMAc solvent were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). It was found that, cellulose was more readily dissolved in [C4mim][CH3COO]/DMAc solvent than in a neat [C4mim][CH3COO], which mainly attributed to the increased "free" [CH3COO](-) anions and [C4mim](+) cations which result from the dissociation of [C4mim][CH3COO] by DMAc. Moreover, the regenerated cellulose from [C4mim][CH3COO]/DMAc solvent displayed good thermostability and similar molecular structure to the original cellulose. PMID:26432363

  9. Multiprobe Spectroscopic Evidence for "Hyperpolarity" within 1-Butyl-3-methylimidazolium Hexafluorophosphate Mixtures with Tetraethylene Glycol

    SciTech Connect

    Sarkar, Abhra; Trivedi, Shruti; Baker, Gary A; Pandey, Siddharth

    2008-01-01

    A hybrid, potentially green solvent system composed of tetraethylene glycol (TEG) and the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]) was investigated across all mole fractions with regard to the solvent properties of the mixture. For this purpose, a suite of absorbance- and fluorescence-based solvatochromic probes were utilized to explore solute-solvent and solvent-solvent interactions existing within the [bmim][PF6] + TEG system. These studies revealed an interesting and unusual synergistic solvent effect. In particular, a remarkable hyperpolarity was observed in which the ET value, comprising dipolarity/polarizability and hydrogen bond donor (HBD) acidity contributions, at intermediate mole fractions of the binary mixture well exceeded that of the most polar pure component (i.e., [bmim][PF6]). Independently determined dipolarity/polarizability ( *) and HBD acidity (R) Kamlet-Taft values for the [bmim][PF6] + TEG mixtures were also observed to be anomalously high at intermediate mole fractions, whereas hydrogen bond acceptor (HBA) basicities ( values) were much more in line with the ideal arithmetic values predicted on a mole fraction basis.

  10. Highly ordered cellulose II crystalline regenerated from cellulose hydrolyzed by 1-butyl-3-methylimidazolium chloride.

    PubMed

    Ahn, Yongjun; Song, Younghan; Kwak, Seung-Yeop; Kim, Hyungsup

    2016-02-10

    This research focused on the preparation of highly ordered cellulose II crystalline by cellulose hydrolysis in ionic liquid, and the influence of molecular mobility on recrystallization of cellulose. The molar mass of cellulose was controlled by hydrolysis using 1-butyl-3-methylimidazolium chloride (BmimCl). The molecular mobility of cellulose dissolved in BmimCl was characterized by rheological properties. After characterization of cellulose solution and regeneration, change of molar mass and conversion to crystalline were monitored using gel-permeation chromatography and powder X-ray diffraction, respectively. The molar mass of the cellulose in BmimCl was remarkably decreased with an increase in duration time, resulting in better mobility and a lower conformational constraint below critical molar mass. The decrease in molar mass surprisingly increased the crystallinity up to ∼ 85%, suggesting a recrystallization rate dependence of the mobility. The correlation between the mobility and recrystallization rate represented quit different behavior above and below a critical molar mass, which strongly demonstrated to the effect of mobility on the conversion of amorphous state to crystalline structure.

  11. Protic acid resin enhanced 1-butyl-3-methylimidazolium chloride pretreatment of Arundo donax Linn.

    PubMed

    You, Tingting; Zhang, Liming; Zhou, Sukun; Xu, Feng

    2014-09-01

    To improve the cellulose digestibility of energy crop Arudo donax Linn. with cost-efficient, a novel pretreatment of protic acid resin Amberlyst 35DRY catalyzed inexpensive ionic liquid (IL) 1-butyl-3-methylimidazolium chloride ([C4mim]Cl) was developed in this work. The pretreatment was performed at 160°C with [C4mim]Cl for 1.5h, followed by Amberlyst 35DRY catalyzed at 90°C for 1h. The IL-Amberlyst pretreatment was demonstrated to be effective, evidenced by the reduction in cellulose crystallinity (31.4%) and increased porosity caused by extensive swelling the undissolved biomass and partial depolymerization of the longer cellulose chain of the dissolved biomass by Amberlyst. Consequently, a higher glucose yield (92.8%) was obtained than for the single [C4mim]Cl pretreatment (42.8%) at an enzyme loading of 20 FPU/g substrate. Overall, the enhanced pretreatment was competitive by using inexpensive and recyclable IL-Amberlyst 35DRY pretreated system with shorter processing time and reduced enzyme usage. PMID:25001325

  12. Understanding the dissolution of cellulose in 1-butyl-3-methylimidazolium acetate+DMAc solvent.

    PubMed

    Xu, Airong; Guo, Xin; Xu, Rui

    2015-11-01

    Cellulose solvent ([C4mim][CH3COO]/DMAc) could be obtained by adding N,N-dimethylacetamide (DMAc) in 1-butyl-3-methylimidazolium acetate ([C4mim][CH3COO]). The solubilities of cellulose in [C4mim][CH3COO]/DMAc solvents were determined at 25°C. The effects of molar ratio of DMAc to [C4mim][CH3COO] on cellulose solubility and the possible dissolution mechanism of cellulose in [C4mim][CH3COO]/DMAc solvent have been studied. Moreover, the regenerated cellulose from [C4mim][CH3COO]/DMAc solvent were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). It was found that, cellulose was more readily dissolved in [C4mim][CH3COO]/DMAc solvent than in a neat [C4mim][CH3COO], which mainly attributed to the increased "free" [CH3COO](-) anions and [C4mim](+) cations which result from the dissociation of [C4mim][CH3COO] by DMAc. Moreover, the regenerated cellulose from [C4mim][CH3COO]/DMAc solvent displayed good thermostability and similar molecular structure to the original cellulose.

  13. Rheological Behaviors of Polyacrylonitrile/1-Butyl-3-Methylimidazolium Chloride Concentrated Solutions

    PubMed Central

    Liu, Weiwei; Cheng, Lingyan; Zhang, Hongyan; Zhang, Yumei; Wang, Huaping; Yu, Mingfang

    2007-01-01

    One of the room temperature ionic liquids (RTILs), 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) was chosen to prepare the concentrated solutions of Polyacrylonitrile (PAN). The rheological behaviors of the solutions were measured with rotational rheometry under different conditions, including temperatures, concentration, and molecular weight of PAN. The solutions exhibited shear-thinning behaviors, similar to that of PAN/DMF solutions. The viscosities decreased with the increasing of shear rates. However, the viscosity decreased sharply at high shear rates when the concentration was up to 16wt%. The dependence of the viscosity on temperature was analyzed through the determination of the apparent activation energy. Unusually, the viscosity of solutions of higher concentration is lower than that of lower concentration. Similarly, the viscosity of low molecular weight PAN was higher than high molecular weight PAN at high shear rates. The dynamic rheological measurement indicates the loss modulus is much higher than storage modulus. The trend of complex viscosity is similar with the result of static rheological measurement. The interaction between PAN and ionic liquid [BMIM]Cl was discussed.

  14. Influence of counterions on micellization of tetramethylammonium perfluorononanoic carboxylate in 1-butyl-3-methylimidazolium ionic liquid.

    PubMed

    Long, Panfeng; Chen, Jingfei; Wang, Dong; Hu, Ziqi; Gao, Xuedong; Li, Ziran; Hao, Jingcheng

    2012-07-01

    The influence of counterions on micellization of perfluorononanoic carboxylate ammonium salts in water and 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim]BF(4)) solutions was investigated by surface tension and (19)F NMR measurements and freeze-fracture transmission electron microscopy (FF-TEM) observations. Changes in the counterions of the fluorocarbon surfactants have different effects on the two solvents. With the increase of counterion volume, the critical micelle concentration (cmc) value of relevant fluorinated surfactant decreases in aqueous solutions. This is because the counterions with larger size, such as (+)N(CH(3))(4), can be little hydrated, which can screen the electrostatic repulsion of the headgroups of the fluorocarbon surfactant and thus facilitate micelle formation. However, the fluorocarbon surfactants can dissolve and form micelles in [bmim]BF(4) only when they provide with largest counterion such as (+)N(CH(3))(4). This is because the counterion, (+)N(CH(3))(4), disperses the charge of the cations, which could weaken the electrostatic interaction between the ion pair of the surfactant, leading to a higher degree of counterion binding. The thermodynamic parameters estimated from the temperature dependence of the cmc values tell us that the micelle formation for tetramethylammonium perfluorononanoic carboxylate (C(8)F(17)COON(CH(3))(4), PFNT) in ionic liquids (ILs) is an entropy-driven process at low temperature but an enthalpy-driven process at high temperature. The driving force of the micellization for fluorocarbon surfactants in [bmim]BF(4) is the solvophobic effect, due to the hydrophobic and oleophobic properties of fluorocarbon chains. PMID:22690854

  15. Aqueous Solutions of the Ionic Liquid 1-butyl-3-methylimidazolium Chloride Denature Proteins

    SciTech Connect

    Baker, Gary A; Heller, William T

    2009-01-01

    As we advance our understanding, ionic liquids (ILs) are finding ever broader scope within the chemical sciences including, most recently, pharmaceutical, enzymatic, and bioanalytical applications. With examples of enzymatic activity reported in both neat ILs and in IL/water mixtures, enzymes are frequently assumed to adopt a quasi-native conformation, even if little work has been carried out to date toward characterizing the conformation, dynamics, active-site perturbation, cooperativity of unfolding transitions, free energy of stabilization, or aggregation/oligomerization state of enzymes in the presence of an IL solvent component. In this study, human serum albumin and equine heart cytochrome c were characterized in aqueous solutions of the fully water-miscible IL 1-butyl-3-methylimidazolium chloride, [bmim]Cl, by small-angle neutron and X-ray scattering. At [bmim]Cl concentrations up to 25 vol.%, these two proteins were found to largely retain their higher-order structures whereas both proteins become highly denatured at the highest IL concentration studied here (i.e., 50 vol.% [bmim]Cl). The response of these proteins to [bmim]Cl is analogous to their behavior in the widely studied denaturants guanidine hydrochloride and urea which similarly lead to random coil conformations at excessive molar concentrations. Interestingly, human serum albumin dimerizes in response to [bmim]Cl, whereas cytochrome c remains predominantly in monomeric form. These results have important implications for enzymatic studies in aqueous IL media, as they suggest a facile pathway through which biocatalytic activity can be altered in these nascent and potentially green electrolyte systems.

  16. Influence of counterions on micellization of tetramethylammonium perfluorononanoic carboxylate in 1-butyl-3-methylimidazolium ionic liquid.

    PubMed

    Long, Panfeng; Chen, Jingfei; Wang, Dong; Hu, Ziqi; Gao, Xuedong; Li, Ziran; Hao, Jingcheng

    2012-07-01

    The influence of counterions on micellization of perfluorononanoic carboxylate ammonium salts in water and 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim]BF(4)) solutions was investigated by surface tension and (19)F NMR measurements and freeze-fracture transmission electron microscopy (FF-TEM) observations. Changes in the counterions of the fluorocarbon surfactants have different effects on the two solvents. With the increase of counterion volume, the critical micelle concentration (cmc) value of relevant fluorinated surfactant decreases in aqueous solutions. This is because the counterions with larger size, such as (+)N(CH(3))(4), can be little hydrated, which can screen the electrostatic repulsion of the headgroups of the fluorocarbon surfactant and thus facilitate micelle formation. However, the fluorocarbon surfactants can dissolve and form micelles in [bmim]BF(4) only when they provide with largest counterion such as (+)N(CH(3))(4). This is because the counterion, (+)N(CH(3))(4), disperses the charge of the cations, which could weaken the electrostatic interaction between the ion pair of the surfactant, leading to a higher degree of counterion binding. The thermodynamic parameters estimated from the temperature dependence of the cmc values tell us that the micelle formation for tetramethylammonium perfluorononanoic carboxylate (C(8)F(17)COON(CH(3))(4), PFNT) in ionic liquids (ILs) is an entropy-driven process at low temperature but an enthalpy-driven process at high temperature. The driving force of the micellization for fluorocarbon surfactants in [bmim]BF(4) is the solvophobic effect, due to the hydrophobic and oleophobic properties of fluorocarbon chains.

  17. Polymer electrolyte based on crosslinked poly(glycidyl methacrylate) and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

    SciTech Connect

    Fei, Beatrice Wong Chui; Hanifah, Sharina Abu; Ahmad, Azizan; Hassan, Nur Hasyareeda

    2015-09-25

    Polymer electrolytes based on crosslinked poly(glycidyl methacrylate) as polymer host and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BmimTFSI) as incorporated salt were prepared by in-situ photopolymerization technique. The complexes with different mass ratio of glycidyl methacrylate (GMA) monomer to BmimTFSI were investigated. The ionic conductivity of the polymer electrolyte was increased and reach the highest value of 7.50 × 10{sup −4} S cm{sup −1} at the ratio of 3:7 (GMA: BmimTFSI). The interaction between the polymer host and ionic liquid was proved by Attenuated Total Reflectance-Fourier Transformation Infra-Red Spectroscopy (ATR-FTIR). Meanwhile, the X-ray diffraction analysis shows the amorphousity of the polymer electrolyte film increase with the ionic liquid ratio.

  18. Comparison and Characterisation of Regenerated Chitosan from 1-Butyl-3-methylimidazolium Chloride and Chitosan from Crab Shells.

    PubMed

    Islam, Saniyat; Arnold, Lyndon; Padhye, Rajiv

    2015-01-01

    Chitosan is a biopolymer derived from chitin which is naturally occurring in the exoskeleton of crustaceans. This paper reports dissolution and regeneration of chitosan by directly dissolving in an ionic liquid solvent, 1-butyl-3-methylimidazolium chloride (BMIMCl). This will provide an ideal platform to solubilise these kinds of polymers to achieve the dissolution. The current study dissolved chitosan from crab shell utilising BMIMCl as a solvent and characterised the resultant regenerated polymer. The regenerated chitosan showed increased hydrogen bonding when characterised by Fourier transform infrared (FTIR) spectral analysis. In addition, the study also compared the characteristics of regenerated and generic chitosan. The regenerated chitosan was also evaluated for antimicrobial properties and showed to possess antibacterial features similar to the commercial grade. This method can be utilised in future for blending of polymers with chitosan in a dissolved phase.

  19. Anomalous Freezing of Nano-Confined Water in Room-Temperature Ionic Liquid 1-Butyl-3-Methylimidazolium Nitrate.

    PubMed

    Abe, Hiroshi; Takekiyo, Takahiro; Yoshimura, Yukihiro; Saihara, Koji; Shimizu, Akio

    2016-04-18

    Non-crystal formation of ice is investigated by simultaneous X-ray diffraction and differential scanning calorimetry measurements upon cooling to -100 °C. At room temperature, size-tunable water confinement (≈20 Å size) in a room-temperature ionic liquid (RTIL, 1-butyl-3-methylimidazolium nitrate, [C4 mim][NO3 ]) exists in a water-rich region (70-90 mol % D2 O). The confined water (water pocket) is characterized by almost monodispersive size distribution. In [C4 mim][NO3 ]-x mol % D2 O (70

  20. Comparison and Characterisation of Regenerated Chitosan from 1-Butyl-3-methylimidazolium Chloride and Chitosan from Crab Shells

    PubMed Central

    Arnold, Lyndon

    2015-01-01

    Chitosan is a biopolymer derived from chitin which is naturally occurring in the exoskeleton of crustaceans. This paper reports dissolution and regeneration of chitosan by directly dissolving in an ionic liquid solvent, 1-butyl-3-methylimidazolium chloride (BMIMCl). This will provide an ideal platform to solubilise these kinds of polymers to achieve the dissolution. The current study dissolved chitosan from crab shell utilising BMIMCl as a solvent and characterised the resultant regenerated polymer. The regenerated chitosan showed increased hydrogen bonding when characterised by Fourier transform infrared (FTIR) spectral analysis. In addition, the study also compared the characteristics of regenerated and generic chitosan. The regenerated chitosan was also evaluated for antimicrobial properties and showed to possess antibacterial features similar to the commercial grade. This method can be utilised in future for blending of polymers with chitosan in a dissolved phase. PMID:26090452

  1. Influence of the current density on the electrochemical treatment of concentrated 1-butyl-3-methylimidazolium chloride solutions on diamond electrodes.

    PubMed

    Marcionilio, Suzana M L de Oliveira; Alves, Gisele M; E Silva, Rachel B Góes; Marques, Pablo J Lima; Maia, Poliana D; Neto, Brenno A D; Linares, José J

    2016-10-01

    This paper focuses on the influence of the current density treatment of a concentrated 1-butyl-3-methylimidazolium chloride (BMImCl) solution on an electrochemical reactor with a boron-doped diamond (BDD) anode. The decrease in the total organic carbon (TOC) and the BMImCl concentration demonstrate the capability of BDD in oxidizing ionic liquids (ILs) and further mineralizing (to CO2 and NO3 (-)) more rapidly at higher current densities in spite of the reduced current efficiency of the process. Moreover, the presence of Cl(-) led to the formation of oxychlorinated anions (mostly ClO3 (-) and ClO4 (-)) and, in combination with the ammonia generated in the cathode from the nitrate reduction, chloramines, more intensely at higher current density. Finally, the analysis of the intermediates formed revealed no apparent influence of the current density on the BMImCl degradation mechanism. The current density presents therefore a complex influence on the IL treatment process that is discussed throughout this paper.

  2. Synthesis, Characterization and Application of 1-Butyl-3 Methylimidazolium Chloride as Green Material for Extractive Desulfurization of Liquid Fuel

    PubMed Central

    Dharaskar, Swapnil A.; Varma, Mahesh N.; Shende, Diwakar Z.; Yoo, Chang Kyoo; Wasewar, Kailas L.

    2013-01-01

    The possible application of imidazolium ionic liquids as energy-efficient green material for extractive deep desulfurization of liquid fuel has been investigated. 1-Butyl-3-methylimidazolium chloride [BMIM]Cl was synthesized by nucleophilic substitution reaction of n-methylimidazolium and 1-chlorobutane. Molecular structures of the ILs were confirmed by FTIR, 1H-NMR, and 13C-NMR. The thermal properties, conductivity, solubility, water content and viscosity analysis of [BMIM]Cl were carried out. The effects of reaction time, reaction temperature, sulfur compounds, and recycling of IL without regeneration on dibenzothiophene removal of liquid fuel were presented. In the extractive desulfurization process, the removal of dibenzothiophene in n-dodecane using [BMIM]Cl was 81% with mass ratio of 1 : 1, in 30 min at 30°C under the mild reaction conditions. Also, desulfurization of real fuels with IL and multistage extraction were studied. The results of this work might offer significant insights in the perceptive use of imidazoled ILs as energy-efficient green material for extractive deep desulfurization of liquid fuels as it can be reused without regeneration with considerable extraction efficiency. PMID:24307868

  3. The genotoxic and cytotoxic effects of 1-butyl-3-methylimidazolium chloride in soil on Vicia faba seedlings.

    PubMed

    Liu, Tong; Zhu, Lusheng; Wang, Jinhua; Wang, Jun; Xie, Hui

    2015-03-21

    Although considered as "green" solvents, the toxic effects of ionic liquids (ILs) on organisms have been widely investigated in recent years. However, studies on the toxic effects of ILs on plants all focus on toxicity in nutrient solution. In the present paper, the toxic effects of 1-butyl-3-methylimidazolium chloride ([C4mim]Cl) on Vicia faba seedlings in soil at 0, 500, 1500, and 2500 mg kg(-1) on day 10 were studied. The present results showed that the growth of V. faba seedlings may be seriously inhibited when the IL concentrations were higher than 500 mg kg(-1). The EC50 values for shoot length, root length, and dry weight were 3886, 2483, and 3359 mg kg(-1), respectively. In addition, [C4mim]Cl caused lipid peroxidation and DNA damage at 500 mg kg(-1) and oxidative stress at 1500 mg kg(-1), which indicated that [C4mim]Cl may have genotoxicity and cytotoxicity on V. faba seedlings. Moreover, oxidative damage may be the main toxic mechanism of ILs.

  4. Catalytic activities of fungal oxidases in hydrophobic ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate-based microemulsion.

    PubMed

    Zhou, Gui-Ping; Zhang, Yun; Huang, Xi-Rong; Shi, Chuan-Hong; Liu, Wei-Feng; Li, Yue-Zhong; Qu, Yin-Bo; Gao, Pei-Ji

    2008-10-01

    For hydrophobic ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF(6)]), an H(2)O-in-[BMIM][PF(6)] microemulsion could be formed in the presence of nonionic surfactant Triton X-100 (TX-100). In such a medium, both lignin peroxidase (LiP) and laccase could express their catalytic activity with the optimum molar ratio of H(2)O to TX-100 at 8.0 for LiP and >20 for laccase, and the optimum pH values at 3.2 for LiP and 4.2 for laccase, respectively. As compared with pure or water saturated [BMIM][PF(6)], in which the two oxidases had negligible catalytic activity due to the strong inactivating effect of [BMIM][PF(6)] on both enzymes, the use of the [BMIM][PF(6)]-based microemulsion had some advantages. Not only the catalytic activities of both fungal oxidases greatly enhanced, but also the apparent viscosity of the medium decreased. PMID:18602799

  5. Structural studies of 1-butyl-3-methylimidazolium tetrafluoroborate/TX-100/ p-xylene ionic liquid microemulsions.

    PubMed

    Gao, Yan'an; Zhang, Jin; Xu, Hongyan; Zhao, Xueyan; Zheng, Liqiang; Li, Xinwei; Yu, Li

    2006-07-17

    The ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF4) forms nonaqueous microemulsions with p-xylene, with the aid of the nonionic surfactant TX-100. The phase behavior of the ternary system is investigated, and three microregions of the microemulsions-ionic liquid-in-oil (IL/O), bicontinuous, and oil-in-ionic liquid (O/IL)-are identified by conductivity measurements, according to percolation theory. On the basis of a phase diagram, a series of IL/O microemulsions are chosen and characterized by dynamic light scattering (DLS). The size of aggregates increases on increasing the amount of added polar component (bmimBF(4)), which is a similar phenomenon to that observed for typical water-in-oil (W/O) microemulsions, suggesting the formation of IL/O microemulsions. The microstructural characteristics of the microemulsions are investigated by FTIR and 1H NMR spectroscopy. The results indicate that the interaction between the electronegative oxygen atoms of the oxyethylene (OE) units in TX-100 and the electropositive imidazolium ring may be the driving force for the solubilization of bmimBF4 into the core of the TX-100 aggregates. In addition, the micropolarity of the microemulsions is investigated by using methyl orange (MO) as a UV/Vis spectroscopic probe. A relatively constant polarity of the microemulsion droplets is obtained in the IL microemulsion. Finally, a plausible structure for the IL/O microemulsion is presented. PMID:16789041

  6. Molecular dynamics simulations of n-hexane at 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide interface

    SciTech Connect

    Lisal, Martin; Izak, Pavel

    2013-07-07

    Molecular dynamics simulations of n-hexane adsorbed onto the interface of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ([bmim][Tf{sub 2}N]) are performed at three n-hexane surface densities, ranged from 0.7 to 2.3 {mu}mol/m{sup 2} at 300 K. For [bmim][Tf{sub 2}N] room-temperature ionic liquid, we use a non-polarizable all-atom force field with the partial atomic charges based on ab initio calculations for the isolated ion pair. The net charges of the ions are {+-}0.89e, which mimics the anion to cation charge transfer and polarization effects. The OPLS-AA force field is employed for modeling of n-hexane. The surface tension is computed using the mechanical route and its value decreases with increase of the n-hexane surface density. The [bmim][Tf{sub 2}N]/n-hexane interface is analyzed using the intrinsic method, and the structural and dynamic properties of the interfacial, sub-interfacial, and central layers are computed. We determine the surface roughness, global and intrinsic density profiles, and orientation ordering of the molecules to describe the structure of the interface. We further compute the survival probability, normal and lateral self-diffusion coefficients, and re-orientation correlation functions to elucidate the effects of n-hexane on dynamics of the cations and anions in the layers.

  7. Determination of the solubility parameter of ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate by inverse gas chromatography.

    PubMed

    Ma, Xiaohong; Wang, Qiang; Li, Xiaoping; Tang, Jun; Zhang, Zhengfang

    2015-11-01

    Thermodynamic properties of ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM] BF4) were determined via inverse gas chromatography (IGC). Two groups of solvents with different chemical natures and polarities were used to obtain information about [BMIM] BF4-solvent interactions. The specific retention volume, molar heat of sorption, weight fraction activity coefficient, Flory-Huggins interaction parameter as well as solubility parameter were also determined in a temperature range of 333 - 373 K. The results showed that the selected solvents n-C10 to n-C12, carbon tetrachloride, cyclohexane and toluene were poor solvents for [BMIM] BF4, while dichloromethane, acetone, chloroform, methyl acetate, ethanol and methanol were favorite solvents for [BMIM] BF4. In addition, the solubility parameter of [ BMIM] BF4 was determined as 23.39 (J/cm3)0.5 by the extrapolation at 298 K. The experiment proved that IGC was a simple and accurate method to obtain the thermodynamic properties of ionic liquids. This study could be used as a reference to the application and research of the ionic liquids. PMID:26939366

  8. Free volume and phase transitions of 1-butyl-3-methylimidazolium based ionic liquids from positron lifetime spectroscopy.

    PubMed

    Yu, Yang; Beichel, Witali; Dlubek, Günter; Krause-Rehberg, Reinhard; Paluch, Marian; Pionteck, Jürgen; Pfefferkorn, Dirk; Bulut, Safak; Friedrich, Christian; Pogodina, Natalia; Krossing, Ingo

    2012-05-21

    Positron annihilation lifetime spectroscopy (PALS) was used to study a series of ionic liquids (ILs) with the 1-butyl-3-methylimidazolium cation ([C4MIM](+)) but different anions [Cl](-), [BF4](-), [PF6](-), [OTf](-), [NTf2](-), and [B(hfip)4](-) with increasing anion volumes. Changes of the ortho-positronium (o-Ps) lifetime parameters with temperature were observed for crystalline and amorphous (glass, supercooled, and normal liquid) states. Evidence for distinct phase transitions, e.g. melting, crystallization and solid-solid transitions, was observed in several PALS experiments. The o-Ps mean lifetime τ3 showed smaller values in the crystalline phase due to dense packing of the material compared to the amorphous phase. The o-Ps lifetime intensity I3 in the liquid state is clearly smaller than in the crystallized state. This behaviour can be attributed to a solvation of e(+) by the anions, which reduces the Ps formation probability in the normal and supercooled liquid. These phenomena were observed for the first time when applying the PALS technique to ionic liquids by us in one preliminary and in this work. Four of the ionic liquids investigated in this work ([BF4](-), [NTf2](-), [PF6](-) and [Cl](-) ILs) exhibit supercooled phases. The specific hole densities and occupied volumes of those ILs were obtained by comparing the local free volume with the specific volume from pressure-volume-temperature (PVT) experiments. From the o-Ps lifetime, the mean size vh of free volume holes of the four samples was calculated and compared with that calculated according to Fürth's hole theory. The hole volumes from both methods agree well. From the Cohen-Turnbull fitting of viscosity and conductivity against PALS/PVT results, the influence of the free volume on molecular transport properties was investigated.

  9. Characterization of the influence of 1-butyl-3-methylimidazolium chloride on the structure and thermal stability of green fluorescent protein

    SciTech Connect

    Heller, William T; O'Neill, Hugh Michael; Zhang, Qiu; Baker, Gary A

    2010-01-01

    Ionic liquids (ILs) are finding a vast array of applications as novel solvents for a wide variety of processes that include enzymatic chemistry, particularly as more biocompatible ILs are designed and discovered. While it is assumed that a native or near-native structure is required for enzymatic activity, there is some evidence that ILs alter protein structure and oligomerization states in a manner than can negatively impact function. The IL 1-butyl-3-methylimidazolium chloride, [bmim]Cl, is a well-studied, water-miscible member of the popular 1-alkyl-3-methylimidazolium IL family. To improve our understanding of the impact of water-miscible ILs on proteins, we have characterized the structure and oligomerization state of green fluorescent protein (GFP) in aqueous solutions containing 25 and 50 vol % [bmim]Cl using a combination of optical spectroscopy and small-angle neutron scattering (SANS). Measurements were also performed as a function of temperature to provide insight into the effect of the IL on the thermal stability of GFP. While GFP exists as a dimer in water, the presence of 25 vol % [bmim]Cl causes GFP to transition to a monomeric state. The SANS data indicate that GFP is a great deal less compact in 50 vol % [bmim]Cl than in neat water, indicative of unfolding from the native structure. The oligomerization state of the protein in IL-containing aqueous solution changes from a dimer to a monomer in response to the IL, but does not change as a function of temperature in the IL-containing solution. The SANS and spectroscopic results also demonstrate that the addition of [bmim]Cl to the solution decreases the thermal stability of GFP, allowing the protein to unfold at lower temperatures than in aqueous solution.

  10. The effect of water on the microstructure of 1-butyl-3-methylimidazolium tetrafluoroborate/TX-100/benzene ionic liquid microemulsions.

    PubMed

    Gao, Yan'an; Li, Na; Zheng, Liqiang; Zhao, Xueyan; Zhang, Jin; Cao, Quan; Zhao, Mingwei; Li, Zhen; Zhang, Gaoyong

    2007-01-01

    The ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]) forms nonaqueous microemulsions with benzene with the aid of nonionic surfactant TX-100. The phase diagram of the ternary system was prepared, and the microstructures of the microemulsion were recognized. On the basis of the phase diagram, a series of ionic liquid-in-oil (IL/O) microemulsions were chosen and characterized by dynamic light scattering (DLS), which shows a similar swelling behavior to typical water-in-oil (W/O) microemulsions. The existence of IL pools in the IL/O microemulsion was confirmed by UV/Vis spectroscopic analysis with CoCl2 and methylene blue (MB) as the absorption probes. A constant polarity of the IL pool is observed, even if small amounts of water are added to the microemulsion, thus suggesting that the water molecules are solubilized in the polar outer shell of the microemulsion, as confirmed by FTIR spectra. 1H NMR spectroscopic analysis shows that these water molecules interact with the electronegative oxygen atoms of the oxyethylene (OE) units of TX-100 through hydrogen-bonding interactions, and the electronegative oxygen atoms of the water molecules attract the electropositive imidazolium rings of [bmim][BF4]. Hence, the water molecules are like a glue that stick the IL and OE units more tightly together and thus make the microemulsion system more stable. Considering the unique solubilization behavior of added water molecules, the IL/O microemulsion system may be used as a medium to prepare porous or hollow nanomaterials by hydrolysis reactions. PMID:17177215

  11. Role of solubilized water in the reverse ionic liquid microemulsion of 1-butyl-3-methylimidazolium tetrafluoroborate/TX-100/benzene.

    PubMed

    Gao, Yan'an; Li, Na; Zheng, Liqiang; Bai, Xiangtao; Yu, Li; Zhao, Xueyan; Zhang, Jin; Zhao, Mingwei; Li, Zhen

    2007-03-15

    The ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF4) can form nonaqueous microemulsions with benzene by the aid of nonionic surfactant TX-100. The effect of water on ionic liquid-in-oil (IL/O) microemulsions was studied, and it was shown that the addition of small amount of water to the IL microemulsion contributed to the stability of microemulsion and thus increased the amount of solubilized bmimBF4 in the microemulsion. The conductivity measurements also showed that the attractive interactions between IL microdroplets were weakened, that is, the IL/O microemulsion becomes more stable in the present of some water. Fourier transform IR was carried out to analyze the states of the added water, and the result showed that these water molecules mainly behaved as bound water and trapped water, indicating that the water molecules are located in the palisade layers of the IL/O microemulsion. Furthermore, 1H NMR and 19F NMR spectra suggested that the added water molecules built the hydrogen binding network of imidazolium cations and H2O, BF4- anion and H2O, and at the same time the electronegative oxygen atoms of the oxyethylene units of TX-100 and water in the palisade layers, which made the palisade layers more firm and thus increased the stability of the microemulsion. The study can help in further understanding the formation mechanism of microemulsions. In addition, the characteristic solubilization behavior of the added water can provide an aqueous interface film for hydrolysis reactions and therefore may be used as an ideal medium to prepare porous or hollow nanomaterials. PMID:17305388

  12. Local Structure in Terms of Nearest-Neighbor Approach in 1-Butyl-3-methylimidazolium-Based Ionic Liquids: MD Simulations.

    PubMed

    Marekha, Bogdan A; Koverga, Volodymyr A; Chesneau, Erwan; Kalugin, Oleg N; Takamuku, Toshiyuki; Jedlovszky, Pál; Idrissi, Abdenacer

    2016-06-01

    Description of the local microscopic structure in ionic liquids (ILs) is a prerequisite to obtain a comprehensive understanding of the influence of the nature of ions on the properties of ILs. The local structure is mainly determined by the spatial arrangement of the nearest neighboring ions. Therefore, the main interaction patterns in ILs, such as cation-anion H-bond-like motifs, cation-cation alkyl tail aggregation, and ring stacking, were considered within the framework of the nearest-neighbor approach with respect to each particular interaction site. We employed classical molecular dynamics (MD) simulations to study in detail the spatial, radial, and orientational relative distribution of ions in a set of imidazolium-based ILs, in which the 1-butyl-3-methylimidazolium (C4mim(+)) cation is coupled with the acetate (OAc(-)), chloride (Cl(-)), tetrafluoroborate (BF4(-)), hexafluorophosphate (PF6(-)), trifluoromethanesulfonate (TfO(-)), or bis(trifluoromethanesulfonyl)amide (TFSA(-)) anion. It was established that several structural properties are strongly anion-specific, while some can be treated as universally applicable to ILs, regardless of the nature of the anion. Namely, strongly basic anions, such as OAc(-) and Cl(-), prefer to be located in the imidazolium ring plane next to the C-H(2/4-5) sites. By contrast, the other four bulky and weakly coordinating anions tend to occupy positions above/below the plane. Similarly, the H-bond-like interactions involving the H(2) site are found to be particularly enhanced in comparison with the ones at H(4-5) in the case of asymmetric and/or more basic anions (C4mimOAc, C4mimCl, C4mimTfO, and C4mimTFSA), in accordance with recent spectroscopic and theoretical findings. Other IL-specific details related to the multiple H-bond-like binding and cation stacking issues are also discussed in this paper. The secondary H-bonding of anions with the alkyl hydrogen atoms of cations as well as the cation-cation alkyl chain

  13. Solvation dynamics in a prototypical ionic liquid + dipolar aprotic liquid mixture: 1-butyl-3-methylimidazolium tetrafluoroborate + acetonitrile.

    PubMed

    Liang, Min; Zhang, Xin-Xing; Kaintz, Anne; Ernsting, Nikolaus P; Maroncelli, Mark

    2014-02-01

    Solvation energies, rotation times, and 100 fs to 20 ns solvation response functions of the solute coumarin 153 (C153) in mixtures of 1-butyl-3-methylimidazolium tetrafluoroborate ([Im41][BF4]) + acetonitrile (CH3CN) at room temperature (20.5 °C) are reported. Available density, shear viscosity, and electrical conductivity data at 25 °C are also collected and parametrized, and new data on refractive indices and component diffusion coefficients presented. Solvation free energies and reorganization energies associated with the S0 ↔ S1 transition of C153 are slightly (≤15%) larger in neat [Im41][BF4] than in CH3CN. No clear evidence for preferential solvation of C153 in these mixtures is found. Composition-dependent diffusion coefficients (D) of Im41(+) and CH3CN as well as C153 rotation times (τ) are approximately related to solution viscosity (η) as D, τ ∝ η(p) with values of p = -0.88, -0.77, and +0.90, respectively. Spectral/solvation response functions (Sν(t)) are bimodal at all compositions, consisting of a subpicosecond fast component followed by a broadly distributed slower component extending over ps-ns times. Integral solvation times (⟨τ(solv)⟩ = ∫(0)(∞)Sν(t) dt) follow a power law on viscosity for mixturecompositions 0.2 ≤ x(IL) ≤ 1 with p = 0.79. With recent broad-band dielectric measurements [J. Phys. Chem. B 2012, 116, 7509] asinput, a simple dielectric continuum model provides predictions for solvation response functions that correctly capture thedistinctive bimodal character of the observed response. At x(IL) ∼ 1 predicted values of ⟨τ(solv)⟩ are smaller than those observed by a factor of 2-3, but the two become approximately equal at x(IL) = 0.2. Predictions of a recent semimolecular theory [J. Phys. Chem. B 2011, 115, 4011] are less accurate, being uniformly slower than the observed solvation dynamics.

  14. Experimental and theoretical investigation of multistage extraction of 1,3-propanediol using the extraction system phosphate/1-butyl-3-methylimidazolium trifluoromethanesulfonate/water.

    PubMed

    Müller, Anja; Lutze, Philip; Górak, Andrzej

    2013-01-01

    The separation of 1,3-propanediol from fermentation broth is a challenging and energy-demanding step using conventional unit operations. One alternative process is the use of an aqueous two-phase system incorporating ionic liquids to use synergy effects of both technologies. Within this manuscript, the technical feasibility of the extraction of 1,3-propanediol using the aqueous two-phase system phosphate (salt)/1-butyl-3-methylimidazolium trifluoromethanesulfonate (ionic liquid)/water in a continuously operated process in pilot-scale is presented. The extraction was performed in a multistage mixer-settler unit and successfully modeled with an equilibrium-stage model and correlations to describe the liquid-liquid equilibrium of the salt/ionic liquid/water two-phase system. The developed and validated model was used for a further investigation of the influence of different process parameters in the determined operating window. Theses parameters include the number of stages, the phase ratio, the pH, and the mass fraction of the involved components. The results prove that the phosphate and 1-butyl-3-methylimidazolium trifluoromethanesulfonate mass fraction, the phase ratio, and the number of stages have a considerable influence on the recovery of 1,3-propanediol, whereas the pH value has only a smaller impact. Those results can be used for optimization of the system as well as for targeting future research within this area.

  15. Melting and freezing behaviors of prototype ionic liquids, 1-butyl-3-methylimidazolium bromide and its chloride, studied by using a nano-Watt differential scanning calorimeter.

    PubMed

    Nishikawa, Keiko; Wang, Shaolan; Katayanagi, Hideki; Hayashi, Satoshi; Hamaguchi, Hiro-o; Koga, Yoshikata; Tozaki, Ken-ichi

    2007-05-10

    1-Butyl-3-methylimidazolium bromide ([bmim]Br) and its chloride ([bmim]Cl) are representative prototypes of ionic liquids. We investigated the melting and freezing behaviors of [bmim]Br and [bmim]Cl by using a homemade differential scanning calorimeter (DSC) with nano-Watt stability and sensitivity. The measurements were carried out at heating and cooling rates slow enough to mimic quasi-static processes. Their thermal behaviors of melting and freezing show characteristic features such as a wide pre-melting range and excessive supercooling and individual behaviors of single crystals even for the same substance. The melting temperatures of [bmim]Br and [bmim]Cl were determined from the broad DSC traces and discussed in relation to the crystal structure. We suggest that the observed characteristics are due to the dynamics of the cooperative change between gauche-trans (GT) and trans-trans (TT) conformations of the butyl group in the [bmim]+ cation.

  16. Physical Properties of Ionic Liquids Consisting of the 1-Butyl-3-Methylimidazolium Cation with Various Anions and the Bis(trifluoromethylsulfonyl)imide Anion with Various Cations

    SciTech Connect

    Jin, Hui; O'Hare, Bernie; Dong, Jing; Arzhantsev, Sergei; Baker, Gary A; Wishart, James F.; Benesi, Alan; Maroncelli, Mark

    2008-01-01

    Physical properties of 4 room-temperature ionic liquids consisting of the 1-butyl-3-methylimidazolium cation with various perfluorinated anions and the bis(trifluoromethylsulfonyl)imide (Tf2N-) anion with 12 pyrrolidinium-, ammonium-, and hydroxyl-containing cations are reported. Electronic structure methods are used to calculate properties related to the size, shape, and dipole moment of individual ions. Experimental measurements of phase-transition temperatures, densities, refractive indices, surface tensions, solvatochromic polarities based on absorption of Nile Red, 19F chemical shifts of the Tf2N- anion, temperature-dependent viscosities, conductivities, and cation diffusion coefficients are reported. Correlations among the measured quantities as well as the use of surface tension and molar volume for estimating Hildebrand solubility parameters of ionic liquids are also discussed.

  17. Interaction between amphiphilic ionic liquid 1-butyl-3-methylimidazolium octyl sulfate and anionic polymer of sodium polystyrene sulfonate in aqueous medium

    NASA Astrophysics Data System (ADS)

    Barhoumi, Z.; Saini, M.; Amdouni, N.; Pal, A.

    2016-09-01

    The micellization of an aqueous solution of the surface active ionic liquid (SAIL), 1-butyl-3-methylimidazolium octylsufate (C4mim)(C8OSO3) and its interaction with an anionic polymer sodium polystyrene sulfonate, (NaPSS) were studied using conductimetry, tensiometry and fluorimetry. Surface tension profile shows a more dramatic increase in the value of surface tension of aqueous (C4mim)(C8OSO3) before the critical micelle concentration (cmc) of IL. The critical micelle concentration (cmc) value of this surfactant was found out from conductance measurements. The thermodynamic parameters, i.e., Gibb's free energy, enthalpy, and entropy of micellization of the IL in aqueous solution have been calculated. Behavior of fluorescence probe confirms the binding interactions between SAIL and the polyelectrolyte.

  18. States of water located in the continuous organic phase of 1-butyl-3-methylimidazolium tetrafluoroborate/Triton X-100/triethylamine reverse microemulsions.

    PubMed

    Li, Na; Cao, Quan; Gao, Yanan; Zhang, Jin; Zheng, Liqiang; Bai, Xiangtao; Dong, Bin; Li, Zhen; Zhao, Mingwei; Yu, Li

    2007-10-22

    We demonstrate a novel ionic liquid (IL) microemulsion, consisting of 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF4) and nonionic surfactant Triton X-100 prepared in triethylamine which is used either as an organic solvent or a Lewis base. The effects of small amounts of added water on the microstructure of the IL microemulsion are investigated by various techniques. UV/Vis spectroscopic analysis and FTIR spectra indicate that these water molecules are not solubilized into the IL pools of the microemulsions. 1H NMR spectra further show that the added water binds with triethylamine to form a surrounding OH- base environment. Some of OH- ions enter the palisade layers of the IL microemulsions and a continuous base interface is created. The unique solubilization behavior of water reveals that it is possible to use the triethylamine microemulsions as a template to prepare metal hydroxides as well as metal oxides in the microemulsions, which is not possible when using traditional microemulsions. PMID:17886245

  19. Effect of 1-Butyl-3-methylimidazolium Halide on the Relative Stability between Sodium Dodecyl Sulfate Micelles and Sodium Dodecyl Sulfate-Poly(ethylene oxide) Nanoaggregates.

    PubMed

    Ferreira, Gabriel M Dias; Ferreira, Guilherme M Dias; Agudelo, Álvaro J Patiño; Hespanhol da Silva, Maria C; Rezende, Jaqueline de Paula; Pires, Ana Clarissa Dos Santos; da Silva, Luis Henrique Mendes

    2015-12-24

    It is well-known that ionic liquids (ILs) alter the properties of aqueous systems containing only surfactants. However, the effect of ILs on polymer-surfactant systems is still unknown. Here, the effect of 1-butyl-3-methylimidazolium bromide (bmimBr) and chloride (bmimCl) on the micellization of sodium dodecyl sulfate (SDS) and its interaction with poly(ethylene oxide) (PEO) was evaluated using conductimetry, fluorimetry, and isothermal titration calorimetry. The ILs decreased the critical micellar concentration (cmc) of the surfactant, stabilizing the SDS micelles. A second critical concentration (c2thc) was verified at high SDS concentrations, due to the micelle size decrease. The stability of PEO/SDS aggregates was also affected by ILs, and the critical aggregation concentration (cac) of SDS increased. Integral aggregation enthalpy changed from -0.72 in water to 2.16 kJ mol(-1) in 4.00 mM bmimBr. IL anions did not affect the SDS micellization or the beginning of PEO/SDS aggregation. Nevertheless, when chloride was replaced with bromide, the amount of SDS bound to the polymer increased. At 100.0 mM IL, the PEO-SDS interaction vanished. We suggest that the effect of ILs comes from participating in the structure of the formed aggregates, interacting with the SDS monomers at the core/interface of the micelles, and promoting preferential solvation of the polymer.

  20. Supercritical carbon dioxide combined with 1-butyl-3-methylimidazolium acetate and ethanol for the pretreatment and enzymatic hydrolysis of sugarcane bagasse.

    PubMed

    Silveira, Marcos Henrique Luciano; Vanelli, Bruno Angelo; Corazza, Marcos Lucio; Ramos, Luiz Pereira

    2015-09-01

    The use of green solvents for the partial delignification of milled sugarcane bagasse (1mm particle size) and for the enhancement of its susceptibility to enzymatic hydrolysis was demonstrated. The experiments were carried out for 2h using 40 g of supercritical carbon dioxide combined with 1-butyl-3-methylimidazolium acetate and 15.8 g of ethanol. The effects of temperature (110-180 °C), pressure (195-250 bar) and IL-to-bagasse mass ratio (0:1-1:1) were investigated through a factorial design in which the response variables were the extent of delignification and both anhydroglucose and anhydroxylose contents in the pretreated materials. The highest delignification degree (41%) led to the best substrate for hydrolysis, giving a 70.7 wt% glucose yield after 12h using 5 wt% and Cellic CTec2® (Novozymes) at 10 mg g(-1) total solids. Hence, excellent substrates for hydrolysis were produced with a minimal IL requirement, which could be recovered by ethanol washing for its downstream processing and reuse. PMID:26056781

  1. Hydrolysis of insoluble cellulose to glucose catalyzed by cellulase-containing liposomes in an aqueous solution of 1-butyl-3-methylimidazolium chloride.

    PubMed

    Yoshimoto, Makoto; Tanimura, Kazuhiko; Tokunaga, Kazuki; Kamimura, Akio

    2013-01-01

    The liposome containing cellulase from Trichoderma viride was prepared under the condition that an appreciable amount of cellulase was incorporated in lipid membranes. The liposomal cellulase and free enzyme were examined in their hydrolytic activities to insoluble cellulose powder CC31 in the acetate buffer solution (pH 4.8) of 15 w/w% [Bmim][Cl] (1-butyl-3-methylimidazolium chloride). The mean diameter and size distribution of cellulase-containing liposome were practically unchanged under the above condition. The free cellulase was deactivated more rapidly than the liposomal cellulase in catalyzing the hydrolysis of 2.0 g/l CC31 at 45°C in the presence of [Bmim][Cl] for 48 h. The activities of liposomal and free cellulase to cellobiose as soluble substrate were less susceptible to [Bmim][Cl] than their cellulolytic activities to CC31, meaning that β-glucosidase is relatively stable among the three enzyme components of cellulase. The rate of glucose production could be appreciably improved by the pretreatment of CC31 with [Bmim][Cl] alone at 120°C for 30 min followed by the liposomal cellulase-catalyzed hydrolysis of the substrate at 45°C at the [Bmim][Cl] concentration of 15 w/w%. PMID:23813807

  2. Electrochemical and Thermodynamic Properties of Ln(III) (Ln = Eu, Sm, Dy, Nd) in 1-Butyl-3-Methylimidazolium Bromide Ionic Liquid

    PubMed Central

    Yang, Xiao; He, Ling; Qin, Song; Tao, Guo-Hong; Huang, Ming; Lv, Yi

    2014-01-01

    The electrochemical behavior and thermodynamic properties of Ln(III) (Ln = Eu, Sm, Dy, Nd) were studied in 1-butyl-3-methylimidazolium bromide ionic liquid (BmimBr) at a glassy carbon (GC) electrode in the range of 293–338 K. The electrode reaction of Eu(III) was found to be quasi-reversible by the cyclic voltammetry, the reactions of the other three lanthanide ions were regarded as irreversible systems. An increase of the current intensity was obtained with the temperature increase. At 293 K, the cathodic peak potentials of −0.893 V (Eu(III)), −0.596 V (Sm(III)), −0.637 V (Dy(III)) and −0.641 V (Nd(III)) were found, respectively, to be assigned to the reduction of Ln(III) to Ln(II). The diffusion coefficients (Do), the transfer coefficients (α) of Ln(III) (Ln = Eu, Sm, Dy, Nd) and the charge transfer rate constants (ks) of Eu(III) were estimated. The apparent standard potential (E0*) and the thermodynamic properties of the reduction of Eu(III) to Eu(II) were also investigated. PMID:24752584

  3. Decrease of droplet size of the reverse microemulsion 1-butyl-3-methylimidazolium tetrafluoroborate/Triton X-100/cyclohexane by addition of water.

    PubMed

    Gao, Yanan; Hilfert, Liane; Voigt, Andreas; Sundmacher, Kai

    2008-03-27

    In the present contribution, results concerning the role of small amounts of water in the 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF4)-in-cyclohexane ionic liquid (IL) reverse microemulsions are reported. Dynamic light scattering (DLS) revealed that the size of microemulsion droplets decreased remarkably with increasing water content although water is often used as a polar component to swell reverse microemulsions. It was thus deduced that the number of microemulsion droplets was increased which was confirmed by conductivity measurements. The states of dissolved water were investigated by Fourier transform IR (FTIR) spectroscopic analysis showing that water molecules mainly act as bound water. 1H NMR along with two-dimensional rotating frame nuclear Overhauser effect (NOE) experiments (ROESY) further revealed that water molecules were mainly located in the periphery of the polar core of the microemulsion droplets and behave like a chock being inserted in the palisade layer of the droplet. This increased the curvature of the surfactant film at the IL/cyclohexane interface and thus led to the decrease of the microemulsion droplet size. The order of surfactant molecules arranged in the interface film was increased and thus induced a loss of entropy. Isothermal titration calorimetry (ITC) indicated that an enthalpy increase compensates for the loss of entropy during the process of microstructural transition. PMID:18318531

  4. Mechanical exfoliation of graphite in 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM-PF6) providing graphene nanoplatelets that exhibit enhanced electrocatalysis

    NASA Astrophysics Data System (ADS)

    Hayes, William Ignatius; Lubarsky, Gennady; Li, Meixian; Papakonstantinou, Pagona

    2014-12-01

    A novel production method for graphene nanoplatelets (GPs) with enhanced electrocatalytic behaviour is presented. GPs show improvement in their oxygen reduction reaction (ORR) catalysis after prolonging the grinding of graphite in 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM-PF6). Nitrogen doping of the GPs has inferred a further increase in ORR. The ORR onset potential, cathodic current magnitude and electron transfer efficiency have all improved as a direct consequence of increasing the graphite grinding duration from 30 min to 4 h. Atomic force microscopy has confirmed a decrease in the GP diameter and height as the grinding increases. Raman spectroscopy indicates a higher level of defects present after prolonging the graphite grinding in BMIM-PF6, most likely a result of the increased edge plane exposure. This increased edge plane appears to promote a higher level of nitrogen incorporation as the graphite grinding duration increases, as confirmed by X-ray photoelectron spectroscopy analysis. The stability of the cathodic current assessed by chronoamperometry analysis is higher for the GP and nitrogen doped graphene nanoplatelet (N-GP) samples than the platinum on carbon black (Pt/C). This study presents a novel process for the production of nitrogen doped graphene nanoplatelets, constituting a strategy for the up-scaled production of electrocatalysts.

  5. Vibrational sum-frequency generation spectroscopy of ionic liquid 1-butyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate at the air-water interface

    NASA Astrophysics Data System (ADS)

    Saha, Ankur; SenGupta, Sumana; Kumar, Awadhesh; Choudhury, Sipra; Naik, Prakash D.

    2016-08-01

    The structure and orientation of room temperature ionic liquid (RTIL) 1-butyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate [PF3(C2F5)3], commonly known as [bmim][fap], have been investigated at the air-[bmim][fap] and air-water interfaces, employing vibrational sum-frequency generation (VSFG) spectroscopy. The VSFG spectra in the CH stretch region suggest presence of the [bmim] cation at the interfaces. Studies reveal that the butyl chain protrudes out into air, and the imidazolium ring lies almost planar to the interface. The CH stretch intensities get enhanced at the air-water interface, mainly because of polar orientation of imidazolium cation induced by interfacial water molecules. The OH stretch intensities are also enhanced at the air-water interface due to polar orientation of interfacial water molecules induced by [bmim][fap]. The Brewster angle microscopy suggests self aggregation of [bmim][fap] in the presence of water, and the aggregation becomes extensive showing dense surface domains with time. However, the surface pressure is almost unaffected due to aggregation.

  6. Supercritical carbon dioxide combined with 1-butyl-3-methylimidazolium acetate and ethanol for the pretreatment and enzymatic hydrolysis of sugarcane bagasse.

    PubMed

    Silveira, Marcos Henrique Luciano; Vanelli, Bruno Angelo; Corazza, Marcos Lucio; Ramos, Luiz Pereira

    2015-09-01

    The use of green solvents for the partial delignification of milled sugarcane bagasse (1mm particle size) and for the enhancement of its susceptibility to enzymatic hydrolysis was demonstrated. The experiments were carried out for 2h using 40 g of supercritical carbon dioxide combined with 1-butyl-3-methylimidazolium acetate and 15.8 g of ethanol. The effects of temperature (110-180 °C), pressure (195-250 bar) and IL-to-bagasse mass ratio (0:1-1:1) were investigated through a factorial design in which the response variables were the extent of delignification and both anhydroglucose and anhydroxylose contents in the pretreated materials. The highest delignification degree (41%) led to the best substrate for hydrolysis, giving a 70.7 wt% glucose yield after 12h using 5 wt% and Cellic CTec2® (Novozymes) at 10 mg g(-1) total solids. Hence, excellent substrates for hydrolysis were produced with a minimal IL requirement, which could be recovered by ethanol washing for its downstream processing and reuse.

  7. Temperature-programed time-of-flight secondary ion mass spectrometry study of 1-butyl-3-methylimidazolium trifluoromethanesulfonate during glass-liquid transition, crystallization, melting, and solvation

    SciTech Connect

    Souda, Ryutaro; Guenster, Jens

    2008-09-07

    For this study, time-of-flight secondary ion mass spectrometry was used to analyze the molecular orientation of 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([bmim][OTf]) and its interaction with the adsorbed Na and LiI species at temperatures of 150-300 K. A glassy [bmim][OTf] film crystallizes at around 230 K, as observed from the increase in the [bmim]{sup +} yield. LiI and Na adsorbed on the glassy film are solvated, whereas they tend to form islands on a crystalline film. The crystalline surface inertness is ascribable to the termination with the CF{sub 3} and C{sub 4}H{sub 9} groups, whereas the exposure of polar SO{sub 3} and imidazole groups at the glassy film results in the solvation. Surface layering occurs during solvation of LiI on the glassy film in such a way that the [bmim]{sup +} ([OTf]{sup -}) moiety is exposed to the vacuum (oriented to the bulk). The LiI adsorbed on the glassy film is incorporated into the bulk at temperatures higher than 200 K because of the glass-liquid transition. No further uptake of LiI is observed during crystallization, providing a contrast to the results of normal molecular solids such as water and ethanol. The surface layers of the crystal melt at temperatures below the bulk melting point, as confirmed from the dissolution of adsorbed LiI, but the melting layer retains a short-range order similar to the crystal. The [bmim][OTf] can be regarded as a strongly correlated liquid with the combined liquid property and crystal-type local structure. The origin of this behavior is discussed.

  8. Electrochemical and spectral properties of ferrocene (Fc) in ionic liquid: 1-butyl-3-methylimidazolium triflimide, [BMIM][NTf(2)]. Concentration effects.

    PubMed

    Vorotyntsev, Mikhail A; Zinovyeva, Veronika A; Konev, Dmitry V; Picquet, Michel; Gaillon, Laurent; Rizzi, Cecile

    2009-01-29

    Several earlier studies of the electrochemical oxidation of ferrocene (Fc) in room-temperature ionic liquids revealed an essentially nonlinear dependence of the oxidation current on the Fc concentration in its relatively dilute solutions, with its formally calculated diffusion coefficient strongly increasing with the concentration. Since no plausible mechanism leading to this very unusual finding had been proposed, our study of Fc solutions in 1-butyl-3-methylimidazolium triflimide, [BMIM][NTf(2)], was performed to verify whether the above observation originated from an incorrect determination of the dissolved Fc concentration. Our observations have demonstrated that reliable control of the Fc concentration in solution is complicated by factors such as the low amount of Fc used to prepare small-volume solutions or the great difficulty to dissolve completely a solid powder in a solvent with an extremely high viscosity. An unexpected additional complication is related to a sufficiently high volatility of Fc which manifests itself even at room temperature and especially at elevated temperatures or/and in the course of vacuum treatment of its solutions or its solid powder. Parallel measurements of electrochemical responses and UV-visible spectra for several series of Fc solutions of various concentrations (prepared with the use of different procedures) have shown a perfect parallelism between the peak current and the intensity of the absorption band in the range of 360-550 nm, leading us to the conclusion of a linear relationship between the oxidation current and the molecularly dissolved Fc concentration. The relations of these measured characteristics with the estimated Fc concentration in these solutions have demonstrated a much greater dispersion (attributed to the difficulty of a precise measurement of the latter) but without a significant deviation from the linearity in general. This finding has allowed us to estimate the diffusion coefficient of this species: D

  9. Solid phase extraction of cadmium on 2-mercaptobenzothiazole loaded on sulfur powder in the medium of ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate and cold vapor generation-atomic absorption spectrometric determination.

    PubMed

    Pourreza, N; Ghanemi, K

    2010-06-15

    A novel solid phase extractor for preconcentration of cadmium at ng L(-1) levels has been developed. Cadmium ions were retained on a column packed with sulfur powder modified with 2-mercaptobenzothiazole (2-MBT) in the medium of 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim](+)PF(6)(-)) ionic liquid. The presence of ionic liquid during modification of sulfur enhanced the retention of cadmium ions on the column. The retained cadmium ions were eluted with 2 mol L(-1) solution of HCl and measured by cold vapor generation-atomic absorption spectrometry (CVG-AAS). By using reaction cell-gas liquid separator (RC-GLS), gaseous cadmium vapors were produced and reached the atomic absorption spectrometer, instantaneously. The influence of different variables on both processes of solid phase extraction and CVG-AAS determination of cadmium ions was investigated. The calibration curve was linear in the range of 10-200 ng L(-1)of cadmium in the initial solution with r=0.9992 (n=8) under optimum conditions. The limit of detection based on three times the standard deviation of the blank (3S(b), n=10) was 4.6 ng L(-1). The relative standard deviation (R.S.D.) of 25 and 150 ng L(-1) of cadmium was 4.1 and 2.2% (n=8), respectively. The procedure was validated by the analysis of a certified reference material (DORM-3), water and fish samples.

  10. Electrochemical reduction of aromatic ketones in 1-butyl-3-methylimidazolium-based ionic liquids in the presence of carbon dioxide: the influence of the ketone substituent and the ionic liquid anion on bulk electrolysis product distribution.

    PubMed

    Zhao, Shu-Feng; Horne, Mike; Bond, Alan M; Zhang, Jie

    2015-07-15

    Electrochemical reduction of aromatic ketones, including acetophenone, benzophenone and 4-phenylbenzophenone, has been undertaken in 1-butyl-3-methylimidazolium-based ionic liquids containing tetrafluoroborate ([BF4](-)), trifluoromethanesulfonate ([TfO](-)) and tris(pentafluoroethyl)trifluorophosphate ([FAP](-)) anions in the presence of carbon dioxide in order to investigate the ketone substituent effect and the influence of the acidic proton on the imidazolium cation (C2-H) on bulk electrolysis product distribution. For acetophenone, the minor products were dimers (<10%) in all ionic liquids, which are the result of acetophenone radical anion coupling. For benzophenone and 4-phenylbenzophenone, no dimers were formed due to steric hindrance. In these cases, even though carboxylic acids were obtained, the main products generated were alcohols (>50%) derived from proton coupled electron transfer reactions involving the electrogenerated radical anions and C2-H. In the cases of both acetophenone and benzophenone, the product distribution is essentially independent of the ionic liquid anion. By contrast, 4-phenylbenzophenone shows a product distribution that is dependent on the ionic liquid anion. Higher yields of carboxylic acids (∼40%) are obtained with [TfO](-) and [FAP](-) anions because in these ionic liquids the C2-H is less acidic, making the formation of alcohol less favourable. In comparison with benzophenone, a higher yield of carboxylic acid (>30% versus ∼15%) was obtained with 4-phenylbenzophenone in all ionic liquids due to the weaker basicity of 4-phenylbenzophenone radical anion.

  11. Partitioning of amino acids in the aqueous biphasic system containing the water-miscible ionic liquid 1-butyl-3-methylimidazolium bromide and the water-structuring salt potassium citrate.

    PubMed

    Zafarani-Moattar, Mohammed Taghi; Hamzehzadeh, Sholeh

    2011-07-01

    In biotechnology, extraction by means of aqueous biphasic systems (ABS) is known as a promising tool for the recovery and purification of bio-molecules. Over the past decade, the increasing emphasis on cleaner and environmentally benign extraction procedures has led to enhanced interest in the ABS containing ionic liquids (ILs)-a new class of non-volatile alternative solvents. ABS composed of the hydrophilic IL {1-butyl-3-methylimidazolium bromide ([C4 mim]Br)} and potassium citrate-which is easily degraded-represents a clean media to green separation of bio-molecules. In this regard, here, the extraction capability of this ABS was evaluated through its application to the extraction of some amino acids. To gain an insight into the driving forces of amino acid partitioning in the studied IL-based ABS, the distribution of five model amino acids (L-tryptophan, L-phenylalanine, L-tyrosine, L-leucine, and L-valine) at different aqueous medium pH values and different phase compositions was investigated. The studies indicated that hydrophobic interactions were the main driving force, although electrostatic interactions and salting-out effects were also important for the transfer of the amino acids. Moreover, based on the statistical analysis of the driving forces of amino acid partitioning in the studied IL-based ABS, a model was established to describe the partition coefficient of three model amino acids, L-tryptophan, L-phenylalanine, and L-valine, and employed to predict the partition coefficient of two other model amino acids, L-tyrosine and L-leucine. PMID:21509956

  12. Molecular mechanism of CO2 and SO2 molecules binding to the air/liquid interface of 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid: A Molecular dynamics study with polarizable potential models

    SciTech Connect

    Wick, Collin D.; Chang, Tsun-Mei; Dang, Liem X.

    2010-11-25

    Molecular dynamics simulations with many-body interactions were carried out to understand the bulk and interfacial absorption of gases in 1-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF4). A new polarizable molecular model was developed for BMIMBF4, which was found to give the correct liquid density, but also had good agreement with experiment for its surface tension and X-ray reflectivity. The potential of mean force of CO2 and SO2 were calculated across the air-BMIMBF4 interface, and the bulk free energies were calculated with the free energy perturbation method. A new polarizable model was also developed for CO2. The air-BMIMBF4 interface had enhanced BMIM density, which was mostly related to its butyl group, followed by enhanced BF4 density a few angstroms towards the liquid bulk. The density profiles were observed to exhibit oscillations between high BMIM and BF4 density, indicating the presence of surface layering induced by the interface. The potential of mean force for CO2 and SO2 showed more negative free energies in regions of enhanced BF4 density, while more positive free energies in regions of high BMIM density. Moreover, these gases showed free energy minimums at the interface, where the BMIM alkyl groups were found to be most prevalent. Our results show the importance of ionic liquid interfacial ordering for understanding gas solvation in them. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  13. Interaction of ionic liquid with water in ternary microemulsions (Triton X-100/water/1-butyl-3-methylimidazolium hexafluorophosphate) probed by solvent and rotational relaxation of coumarin 153 and coumarin 151.

    PubMed

    Seth, Debabrata; Chakraborty, Anjan; Setua, Palash; Sarkar, Nilmoni

    2006-08-29

    The interaction of ionic liquid with water in 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6])/Triton X-100 (TX-100)/H2O ternary microemulsions, i.e., "[bmim][PF6]-in-water" microregions of the microemulsions, has been studied by the dynamics of solvent and rotational relaxation of coumarin 153 (C-153) and coumarin 151 (C-151). The variation of the time constants of solvent relaxation of C-153 is very small with an increase in the [bmim][PF6]/TX-100 ratio (R). The rotational relaxation time of C-153 also remains unchanged in all micremulsions of different R values. The invariance of solvation and rotational relaxation times of C-153 indicates that the position of C-153 remains unaltered with an increase in R and probably the probe is located at the interfacial region of [bmim][PF6] and TX-100 in the microemulsions. On the other hand, in the case of C-151, with an increase in R the fast component of the solvation time gradually increases and the slow component gradually decreases, although the change in solvation time is small in comparison to that of microemulsions containing common polar solvents such as water, methanol, acetonitrile, etc. The rotational relaxation time of C-151 increases with an increase in R. This indicates that with an increase in the [bmim][PF6] content the number of C-151 molecules in the core of the microemulsions gradually increases. In general, the solvent relaxation time is retarded in this room temperature ionic liquid/water-containing microemulsion compared to that of a neat solvent, although retardation is very small compared to that of the solvent relaxation time of the conventional solvent in the core of the microemulsions. PMID:16922562

  14. Pretreatment and fractionation of wheat straw using various ionic liquids.

    PubMed

    Lopes, André M da Costa; João, Karen G; Bogel-Łukasik, Ewa; Roseiro, Luísa B; Bogel-Łukasik, Rafał

    2013-08-21

    Pretreatment of lignocellulosic biomass with ionic liquids (ILs) is a promising and challenging process for an alternative method of biomass processing. The present work emphasizes the examination of wheat straw pretreatment using ILs, namely, 1-butyl-3-methylimidazolium hydrogensulfate ([bmim][HSO4]), 1-butyl-3-methylimidazolium thiocyanate ([bmim][SCN]), and 1-butyl-3-methylimidazolium dicyanamide ([bmim][N(CN)2]). Only [bmim][HSO4] was found to achieve a macroscopic complete dissolution of wheat straw during pretreatment. The fractionation process demonstrated to be dependent on the IL used. Using [bmim][SCN], a high-purity lignin-rich material was obtained. In contrast, [bmim][N(CN)2] was a good solvent to produce high-purity carbohydrate-rich fractions. When [bmim][HSO4] was used, a different behavior was observed, exhibiting similarities to an acid hydrolysis pretreatment, and no hemicellulose-rich material was recovered during fractionation. A capillary electrophoresis (CE) technique allowed for a better understanding of this phenomenon. Hydrolysis of carbohydrates was confirmed, although an extended degradation of monosaccharides to furfural and hydroxymethylfurfural (HMF) was observed.

  15. Distribution of 1-Butyl-3-methylimidazolium Bistrifluoromethylsulfonimide in Mesoporous Silica as a Function of Pore Filling

    SciTech Connect

    Han, Kee Sung; Wang, Xiqing; Hagaman, Edward {Ed} W; Dai, Sheng

    2013-01-01

    Rotational dynamics of the ionic liquid (IL) 1-butyl-3-methlyimidazolium bistrifluoromethylsulfonimide, [C4mim][Tf2N], 1, as a neat liquid and confined in mesoporous silica were investigated by 1H spin-spin (T2) and spin-lattice (T1) relaxation measurements and 13C NMR spectroscopy. Translational dynamics (self-diffusion) were monitored via the diffusion coefficient, D, obtained with 1H pulsed field gradient NMR measurements. These data were used to determine the distribution of 1 in the pores of KIT-6, a mesoporous silica with a bicontinuous gyroid pore structure, as a function of filling fraction. Relaxation studies performed as a function of filling factor and temperature, reveal a dynamic heterogeneity in both translational and rotational motions for 1 at filling factors, f, = 0.2-1.0 (f = 1 corresponds to fully filled pores). Spin-lattice and spin-spin relaxation times reveal the motion of 1 in silica mesopores conform to that expected for a two-dimensional relaxation model. The relaxation dynamics are interpreted using a two-state, fast exchange model for all motions; a slow rotation (and translation) of molecules in contact with the surface and a faster motion approximated by the values for bulk relaxation and diffusion. 1 retains liquid like behavior at all filling factors and temperatures that extend to ca. 50 degrees below the bulk melting point. Translational motion in these systems, interpreted with MD-simulated diffusivity limits, confirms the high propensity of 1 to form a monolayer film on the silica surface at low filling factors.. The attractive interaction of 1 with the surface is greater than that for self-association of 1. The trends in diffusion data at short and long diffusion time suggest that the population of surface-bound 1 is in intimate contact with 1 in the pores. This condition is most easily met at higher filling fractions with successive additions of 1 increasing the layer thickness built up on the surface layer.

  16. ALPHA-AMYLASE ACTIVITY IN VARIOUS CONCENTRATIONS OF THE IONIC LIQUID, 1-BUTYL-3-METHYLIMIDAZOLIUM CHLORIDE

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Starch is an extremely abundant, economical and versatile industrial commodity. Many industrial uses of starch depend on hydrolyzing the polymer for the conversion of glucose and maltodextrins. Starch hydrolysis is frequently achieved by utilizing alpha-amylase, which is an endo-acting enzyme that...

  17. Volumetric properties of binary mixtures of benzene with cyano-based ionic liquids

    NASA Astrophysics Data System (ADS)

    Gonfa, Girma; Bustam, Mohamad Azmi; Moniruzzaman, Muhammad; Murugesan, Thanabalan

    2014-10-01

    The objective of this study is to investigate the volumetric properties of the binary mixtures comprised benzene and two ionic liquids, 1-butyl-3-methylimidazolium thiocyanate ([BMIM][SCN]) and 1-butyl-3-methyl- imidazolium dicyanamide ([ BMIM ][ N ( CN )2]( . Densities (ρ) and viscosities (μ) of the binary mixtures were measured over a temperature range of 293.15 to 323.15 K and at atmospheric pressure. Excess molar volumes and viscosity deviations were calculated from the experimental densities and viscosities values. The volumetric properties of the mixtures were changed significantly with the change of compositions and temperatures. It was also found that the value of excess molar volume and viscosity deviations were negative (-ve) over the entire range of compositions. The results have been interpreted in terms of molecular interactions of ILs and benzene.

  18. CRYSTAL POLYMORPHISM IN 1-BUTYL-3-METHYLIMIDAZOLIUM HALIDES: SUPPORTING IONIC LIQUID FORMATION THROUGH INHIBITION OF CRYSTALLIZATION. (R828257)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  19. Adsorption of 1-butyl-3-methylimidazolium chloride ionic liquid by functional carbon microspheres from hydrothermal carbonization of cellulose.

    PubMed

    Qi, Xinhua; Li, Luyang; Tan, Tengfei; Chen, Wenting; Smith, Richard L

    2013-03-19

    Functional carbonaceous material (FCM) loaded with carboxylic groups was prepared by hydrothermal carbonization of cellulose in the presence of acrylic acid. The resulting FCM was used as adsorbent for recovery of a water-soluble ionic liquid, 1-butyl-3-methyl-imidazolium chloride ([BMIM][Cl]). The FCM consisted of microspheres (100-150 nm) and had a low surface area (ca. 20 m(2)/g), but exhibited adsorption capacity comparable to that of commercial activated carbon which can be attributed to the presence of high content of polar oxygenated groups (-OH, -C═O, -COOH) as revealed by spectral analyses. Sorption of [BMIM][Cl] onto FCM adsorbent could be well-described by pseudo-second-order kinetics. Thermodynamic and adsorption isothermal analyses revealed that the adsorption process was spontaneous, exothermic, and could be described by the Freundlich adsorption model. The FCM adsorbent could be regenerated effectively and recycled for at least three times without loss of adsorption capacity. The results of this work provide a facile method for production of functional carbonaceous materials from renewable resources that can be used for treatment of aqueous streams containing small concentrations of ionic liquid, [BMIM][Cl]. PMID:23410095

  20. Adsorption of 1-butyl-3-methylimidazolium chloride ionic liquid by functional carbon microspheres from hydrothermal carbonization of cellulose.

    PubMed

    Qi, Xinhua; Li, Luyang; Tan, Tengfei; Chen, Wenting; Smith, Richard L

    2013-03-19

    Functional carbonaceous material (FCM) loaded with carboxylic groups was prepared by hydrothermal carbonization of cellulose in the presence of acrylic acid. The resulting FCM was used as adsorbent for recovery of a water-soluble ionic liquid, 1-butyl-3-methyl-imidazolium chloride ([BMIM][Cl]). The FCM consisted of microspheres (100-150 nm) and had a low surface area (ca. 20 m(2)/g), but exhibited adsorption capacity comparable to that of commercial activated carbon which can be attributed to the presence of high content of polar oxygenated groups (-OH, -C═O, -COOH) as revealed by spectral analyses. Sorption of [BMIM][Cl] onto FCM adsorbent could be well-described by pseudo-second-order kinetics. Thermodynamic and adsorption isothermal analyses revealed that the adsorption process was spontaneous, exothermic, and could be described by the Freundlich adsorption model. The FCM adsorbent could be regenerated effectively and recycled for at least three times without loss of adsorption capacity. The results of this work provide a facile method for production of functional carbonaceous materials from renewable resources that can be used for treatment of aqueous streams containing small concentrations of ionic liquid, [BMIM][Cl].

  1. Ionic liquid 1-butyl-3-methylimidazolium cyanamide (bmim [dca]) as a solvent and catalyst for acylation of maltodextrin

    Technology Transfer Automated Retrieval System (TEKTRAN)

    We have found a novel method to prepare maltodextrin stearate with DS upto 0.60 in 90% yields from maltodextrin in IL bmim[dca] reacted with vinyl stearate or stearic acid. In this work we have demonstrated that IL could simultaneously act as a solvent and as a catalyst for reaction of maltodextrin...

  2. Catalytic dimerization of propene by nickel-phosphine complexes in 1-butyl-3-methylimidazolium chloride/AlEt{sub x}Cl{sub 3{minus}x} (x = 0, 1) ionic liquids

    SciTech Connect

    Chauvin, Y.; Einloft, S.; Olivier, H.

    1995-04-01

    The dimerization of propene was catalyzed by cationic nickel complexes in a two-phase solvent system using organochloroaluminate ionic liquids as the solvent for the catalyst. In ionic liquids containing an excess of strongly coordinating chloride ions, i.e., basic, no activity was observed. In contrast, melts containing an excess of alkylchloroaluminum species, i.e., acidic, stabilized the active cationic nickel species. The reaction products separate as an organic layer. Molecular organochloroaluminum species were extracted, and the composition of the salt was strongly modified. This was circumvented using a salt which contains an excess of aluminum chloride. The propene dimers obtained by this way can be transformed either into ethers or into alkanes to produce high octane number additives for gasoline. The effects of phosphine ligands coordinated on nickel and operating variables were investigated in order to maximize the octane number of the corresponding alkanes and ethers.

  3. Microbial Thiocyanate Utilization under Highly Alkaline Conditions

    PubMed Central

    Sorokin, Dimitry Y.; Tourova, Tatyana P.; Lysenko, Anatoly M.; Kuenen, J. Gijs

    2001-01-01

    Three kinds of alkaliphilic bacteria able to utilize thiocyanate (CNS−) at pH 10 were found in highly alkaline soda lake sediments and soda soils. The first group included obligate heterotrophs that utilized thiocyanate as a nitrogen source while growing at pH 10 with acetate as carbon and energy sources. Most of the heterotrophic strains were able to oxidize sulfide and thiosulfate to tetrathionate. The second group included obligately autotrophic sulfur-oxidizing alkaliphiles which utilized thiocyanate nitrogen during growth with thiosulfate as the energy source. Genetic analysis demonstrated that both the heterotrophic and autotrophic alkaliphiles that utilized thiocyanate as a nitrogen source were related to the previously described sulfur-oxidizing alkaliphiles belonging to the gamma subdivision of the division Proteobacteria (the Halomonas group for the heterotrophs and the genus Thioalkalivibrio for autotrophs). The third group included obligately autotrophic sulfur-oxidizing alkaliphilic bacteria able to utilize thiocyanate as a sole source of energy. These bacteria could be enriched on mineral medium with thiocyanate at pH 10. Growth with thiocyanate was usually much slower than growth with thiosulfate, although the biomass yield on thiocyanate was higher. Of the four strains isolated, the three vibrio-shaped strains were genetically closely related to the previously described sulfur-oxidizing alkaliphiles belonging to the genus Thioalkalivibrio. The rod-shaped isolate differed from the other isolates by its ability to accumulate large amounts of elemental sulfur inside its cells and by its ability to oxidize carbon disulfide. Despite its low DNA homology with and substantial phenotypic differences from the vibrio-shaped strains, this isolate also belonged to the genus Thioalkalivibrio according to a phylogenetic analysis. The heterotrophic and autotrophic alkaliphiles that grew with thiocyanate as an N source possessed a relatively high level of cyanase

  4. Microbial thiocyanate utilization under highly alkaline conditions.

    PubMed

    Sorokin, D Y; Tourova, T P; Lysenko, A M; Kuenen, J G

    2001-02-01

    Three kinds of alkaliphilic bacteria able to utilize thiocyanate (CNS-) at pH 10 were found in highly alkaline soda lake sediments and soda soils. The first group included obligate heterotrophs that utilized thiocyanate as a nitrogen source while growing at pH 10 with acetate as carbon and energy sources. Most of the heterotrophic strains were able to oxidize sulfide and thiosulfate to tetrathionate. The second group included obligately autotrophic sulfur-oxidizing alkaliphiles which utilized thiocyanate nitrogen during growth with thiosulfate as the energy source. Genetic analysis demonstrated that both the heterotrophic and autotrophic alkaliphiles that utilized thiocyanate as a nitrogen source were related to the previously described sulfur-oxidizing alkaliphiles belonging to the gamma subdivision of the division Proteobacteria (the Halomonas group for the heterotrophs and the genus Thioalkalivibrio for autotrophs). The third group included obligately autotrophic sulfur-oxidizing alkaliphilic bacteria able to utilize thiocyanate as a sole source of energy. These bacteria could be enriched on mineral medium with thiocyanate at pH 10. Growth with thiocyanate was usually much slower than growth with thiosulfate, although the biomass yield on thiocyanate was higher. Of the four strains isolated, the three vibrio-shaped strains were genetically closely related to the previously described sulfur-oxidizing alkaliphiles belonging to the genus Thioalkalivibrio. The rod-shaped isolate differed from the other isolates by its ability to accumulate large amounts of elemental sulfur inside its cells and by its ability to oxidize carbon disulfide. Despite its low DNA homology with and substantial phenotypic differences from the vibrio-shaped strains, this isolate also belonged to the genus Thioalkalivibrio according to a phylogenetic analysis. The heterotrophic and autotrophic alkaliphiles that grew with thiocyanate as an N source possessed a relatively high level of cyanase

  5. Solvent extraction behaviour of thiocyanic acid.

    PubMed

    Jurriaanse, A; Kemp, D M

    1968-11-01

    The solvent extraction behaviour of thiocyanic acid with isobutyl methyl ketone and xylene as solvents is described. In the ketone system the thiocyanic acid is solvated in the organic phase to give a complex with a proposed composition of HSCN. 2IBMK. Deviations from ideal behaviour, which can be attributed to variations in the activity coefficient of the acid in the aqueous phase, are shown.

  6. 21 CFR 558.248 - Erythromycin thiocyanate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL DRUGS, FEEDS, AND RELATED PRODUCTS NEW ANIMAL DRUGS FOR USE IN ANIMAL FEEDS Specific New Animal Drugs for Use in Animal Feeds § 558.248 Erythromycin thiocyanate. (a) Approvals. Type A medicated...

  7. Understanding chemical reactions of CO2 and its isoelectronic molecules with 1-butyl-3-methylimidazolium acetate by changing the nature of the cation: the case of CS2 in 1-butyl-1-methylpyrrolidinium acetate studied by NMR spectroscopy and density functional theory calculations.

    PubMed

    Cabaço, M Isabel; Besnard, Marcel; Chávez, Fabián Vaca; Pinaud, Noël; Sebastião, Pedro J; Coutinho, João A P; Danten, Yann

    2014-06-28

    NMR spectroscopy ((1)H, (13)C, (15)N) shows that carbon disulfide reacts spontaneously with 1-butyl-1-methylpyrrolidinium acetate ([BmPyrro][Ac]) in the liquid phase. It is found that the acetate anions play an important role in conditioning chemical reactions with CS2 leading, via coupled complex reactions, to the degradation of this molecule to form thioacetate anion (CH3COS(-)), CO2, OCS, and trithiocarbonate (CS3 (2-)). In marked contrast, the cation does not lead to the formation of any adducts allowing to conclude that, at most, its role consists in assisting indirectly these reactions. The choice of the [BmPyrro](+) cation in the present study allows disentangling the role of the anion and the cation in the reactions. As a consequence, the ensemble of results already reported on CS2-[Bmim][Ac] (1), OCS-[Bmim][Ac] (2), and CO2-[Bmim][Ac] (3) systems can be consistently rationalized. It is argued that in system (1) both anion and cation play a role. The CS2 reacts with the acetate anion leading to the formation of CH3COS(-), CO2, and OCS. After these reactions have proceeded the nascent CO2 and OCS interact with the cation to form imidazolium-carboxylate ([Bmim] CO2) and imidazolium-thiocarboxylate ([Bmim] COS). The same scenario also applies to system (2). In contrast, in the CO2-[Bmim] [Ac] system a concerted cooperative process between the cation, the anion, and the CO2 molecule takes place. A carbene issued from the cation reacts to form the [Bmim] CO2, whereas the proton released by the ring interacts with the anion to produce acetic acid. In all these systems, the formation of adduct resulting from the reaction between the solute molecule and the carbene species originating from the cation is expected. However, this species was only observed in systems (2) and (3). The absence of such an adduct in system (1) has been theoretically investigated using DFT calculations. The values of the energetic barrier of the reactions show that the formation of [Bmim] CS2 is unfavoured and that the anion offers a competitive reactive channel via an oxygen-sulphur exchange mechanism with the solute in systems (1) and (2).

  8. Understanding chemical reactions of CO{sub 2} and its isoelectronic molecules with 1-butyl-3-methylimidazolium acetate by changing the nature of the cation: The case of CS{sub 2} in 1-butyl-1-methylpyrrolidinium acetate studied by NMR spectroscopy and density functional theory calculations

    SciTech Connect

    Cabaço, M. Isabel; Besnard, Marcel; Danten, Yann; Chávez, Fabián Vaca; Pinaud, Noël; Sebastião, Pedro J.; Coutinho, João A. P.

    2014-06-28

    NMR spectroscopy ({sup 1}H, {sup 13}C, {sup 15}N) shows that carbon disulfide reacts spontaneously with 1-butyl-1-methylpyrrolidinium acetate ([BmPyrro][Ac]) in the liquid phase. It is found that the acetate anions play an important role in conditioning chemical reactions with CS{sub 2} leading, via coupled complex reactions, to the degradation of this molecule to form thioacetate anion (CH{sub 3}COS{sup −}), CO{sub 2}, OCS, and trithiocarbonate (CS{sub 3}{sup 2−}). In marked contrast, the cation does not lead to the formation of any adducts allowing to conclude that, at most, its role consists in assisting indirectly these reactions. The choice of the [BmPyrro]{sup +} cation in the present study allows disentangling the role of the anion and the cation in the reactions. As a consequence, the ensemble of results already reported on CS{sub 2}-[Bmim][Ac] (1), OCS-[Bmim][Ac] (2), and CO{sub 2}-[Bmim][Ac] (3) systems can be consistently rationalized. It is argued that in system (1) both anion and cation play a role. The CS{sub 2} reacts with the acetate anion leading to the formation of CH{sub 3}COS{sup −}, CO{sub 2}, and OCS. After these reactions have proceeded the nascent CO{sub 2} and OCS interact with the cation to form imidazolium-carboxylate ([Bmim] CO{sub 2}) and imidazolium-thiocarboxylate ([Bmim] COS). The same scenario also applies to system (2). In contrast, in the CO{sub 2}-[Bmim] [Ac] system a concerted cooperative process between the cation, the anion, and the CO{sub 2} molecule takes place. A carbene issued from the cation reacts to form the [Bmim] CO{sub 2}, whereas the proton released by the ring interacts with the anion to produce acetic acid. In all these systems, the formation of adduct resulting from the reaction between the solute molecule and the carbene species originating from the cation is expected. However, this species was only observed in systems (2) and (3). The absence of such an adduct in system (1) has been theoretically investigated using DFT calculations. The values of the energetic barrier of the reactions show that the formation of [Bmim] CS{sub 2} is unfavoured and that the anion offers a competitive reactive channel via an oxygen-sulphur exchange mechanism with the solute in systems (1) and (2)

  9. Wet oxidation of real coke wastewater containing high thiocyanate concentration.

    PubMed

    Oulego, Paula; Collado, Sergio; Garrido, Laura; Laca, Adriana; Rendueles, Manuel; Díaz, Mario

    2014-01-01

    Coke wastewaters, in particular those with high thiocyanate concentrations, represent an important environmental problem because of their very low biodegradability. In this work, the treatment by wet oxidation of real coke wastewaters containing concentrations of thiocyanate above 17 mM has been studied in a 1-L semi-batch reactor at temperatures between 453 and 493 K, with total oxygen pressures in the range of 2.0-8.0 MPa. A positive effect of the matrix of real coke wastewater was observed, resulting in faster thiocyanate degradation than was obtained with synthetic wastewaters. Besides, the effect of oxygen concentration and temperature on thiocyanate wet oxidation was more noticeable in real effluents than in synthetic wastewaters containing only thiocyanate. It was also observed that the degree of mineralization of the matrix organic compounds was higher when the initial thiocyanate concentration increased. Taking into account the experimental data, kinetic models were obtained, and a mechanism implying free radicals was proposed for thiocyanate oxidation in the matrix considered. In all cases, sulphate, carbonates and ammonium were identified as the main reaction products of thiocyanate wet oxidation.

  10. Thiocyanate as a marker of saliva in gastric juice?

    PubMed Central

    Boulos, P B; Whitfield, P F; Dave, M; Faber, R G; Hobsley, M

    1980-01-01

    One source of error in gastric secretion studies is swallowed saliva. The possibility that salivary thiocyanate might be used to measure this contamination has been investigated. Thiocyanate concentration was measured in saliva and gastric juice collected simultaneously in 22 duodenal ulcer patients undergoing routine insulin and histamine secretion studies. On stimulation, despite the increase in the rate of gastric secretion this was not matched by an appropriate fall in the concentration of thiocyanate in gastric juice. Moreover, in one-third of the gastric juice specimens, the thiocyanate concentration was greater than in the simultaneous samples of saliva. Thus, contrary to what has been claimed, thiocyanate is present not only in saliva but also in gastric juice. Therefore it cannot be used as a marker of salivary contamination. An adequate marker of this source of error has not yet been found. PMID:6988302

  11. Thiocyanate hydrolase, the primary enzyme initiating thiocyanate degradation in the novel obligately chemolithoautotrophic halophilic sulfur-oxidizing bacterium Thiohalophilus thiocyanoxidans.

    PubMed

    Bezsudnova, Ekaterina Yu; Sorokin, Dimitry Yu; Tikhonova, Tamara V; Popov, Vladimir O

    2007-12-01

    Thiohalophilus thiocyanoxidans is a first halophilic sulfur-oxidizing chemolithoautotrophic bacterium capable of growth with thiocyanate as an electron donor at salinity up to 4 M NaCl. The cells, grown with thiocyanate, but not with thiosulfate, contained an enzyme complex hydrolyzing thiocyanate to sulfide and ammonia under anaerobic conditions with carbonyl sulfide as an intermediate. Despite the fact of utilization of the , high cyanase activity was also detected in thiocyanate-induced cells. Three-stage column chromotography resulted in a highly purified thiocyanate-hydrolyzing protein with an apparent molecular mass of 140 kDa that consists of three subunits with masses 17, 19 and 29 kDa. The enzyme is a Co,Fe-containing protein resembling on its function and subunit composition the enzyme thiocyanate hydrolase from the Betaproteobacterium Thiobacillus thioparus. Cyanase, copurified with thiocyanate hydrolase, is a bisubstrate multisubunit enzyme with an apparent subunit molecular mass of 14 kDa. A possible role of cyanase in thiocyanate degradation by T. thiocyanoxidans is discussed.

  12. LABORATORY DETECTION OF THIOCYANIC ACID HSCN

    SciTech Connect

    Bruenken, S.; Yu, Z.; Gottlieb, C. A.; McCarthy, M. C.; Thaddeus, P. E-mail: cgottlieb@cfa.harvard.ed E-mail: pthaddeus@cfa.harvard.ed

    2009-12-01

    The rotational spectrum of thiocyanic acid HSCN, a highly polar isomer of the well-known astronomical molecule isothiocyanic acid HNCS, has been measured in two radio bands: in the centimeter-wave band by Fourier transform microwave spectroscopy in a molecular beam, and in the millimeter-wave band by long-path absorption spectroscopy in a low-pressure glow discharge. Twelve spectroscopic constants were derived from more than 60 a-type rotational transitions between 11 and 346 GHz with J up to 30 and K{sub a} <= 6, including seven centimeter-wave transitions with resolved hyperfine structure. With these constants the rotational spectrum in the K{sub a} = 0 and K{sub a} = 1 ladders-those most likely to be observed in space-can now be calculated up to 400 GHz with formal uncertainties of less than 0.2 km s{sup -1} in equivalent radial velocity. Thiocyanic acid was recently identified in Sgr B2 by Halfen et al. following the laboratory measurements, and there is possible evidence for it in cold dark clouds, with the implication that HSCN may be detectable in many galactic sources.

  13. General and practical formation of thiocyanates from thiols.

    PubMed

    Frei, Reto; Courant, Thibaut; Wodrich, Matthew D; Waser, Jerome

    2015-02-01

    A new method for the cyanation of thiols and disulfides using cyanobenziodoxol(on)e hypervalent iodine reagents is described. Both aliphatic and aromatic thiocyanates can be accessed in good yields in a few minutes at room temperature starting from a broad range of thiols with high chemioselectivity. The complete conversion of disulfides to thiocyanates was also possible. Preliminary computational studies indicated a low energy concerted transition state for the cyanation of the thiolate anion or radical. The developed thiocyanate synthesis has broad potential for various applications in synthetic chemistry, chemical biology and materials science.

  14. Copper thiocyanate: polytypes, defects, impurities, and surfaces.

    PubMed

    Tsetseris, Leonidas

    2016-07-27

    Copper thiocyanate (CuSCN) is an established solid state dye in solar cells and has emerged as a key material for applications in transparent conductors and solution-processed thin film transistors. Here we report the results of density-functional theory calculations on several fundamental properties related to the performance of CuSCN in the above-mentioned systems. We describe the structural and electronic properties of CuSCN phases and show that the material is prone to polytypism. We also perform a systematic study on various defects and hydrogen impurities and determine their effect on the electronic properties of the host system, particularly with respect to doping. Finally, we show that non-polar surfaces have low formation energies, suggesting easy cleavage along certain directions. PMID:27248787

  15. Environmental Perchlorate and Thiocyanate Exposures and Infant Serum Thyroid Function

    PubMed Central

    Braverman, Lewis E.; He, Xuemei; Schuller, Kristin E.; Roussilhes, Alexandra; Jahreis, Katherine A.; Pearce, Elizabeth N.

    2012-01-01

    Background Breastfed infants rely on maternal iodine for thyroid hormone production required for neurodevelopment. Dietary iodine among women of childbearing age in the United States may be insufficient. Perchlorate (competitive inhibitor of the sodium/iodide symporter [NIS]) exposure is ubiquitous. Thiocyanate, from cigarettes and diet, is a weaker NIS inhibitor. Environmental perchlorate and thiocyanate exposures could decrease breast milk iodine by competitively inhibiting NIS in lactating breasts (thus impairing infants' iodine availability), and/or infants' thyroidal NIS to directly decrease infant thyroid function. The current study assessed the relationships between environmental perchlorate and thiocyanate exposures and infant serum thyroid function. Methods Iodine, perchlorate, and thiocyanate in breast milk, maternal and infant urine, and infant serum thyroid function tests were cross-sectionally measured in Boston-area women and their 1–3 month-old breastfed infants. Univariate and multivariable analyses assessed relationships between iodine, perchlorate, thiocyanate, thyroid-stimulating hormone (TSH), and free thyroxine (FT4) levels. Results In 64 mothers and infants, median (range) iodine levels were 45.6 μg/L (4.3–1080) in breast milk, 101.9 μg/L (27–570) in maternal urine, and 197.5 μg/L (40–785) in infant urine. Median perchlorate concentrations were 4.4 μg/L (0.5–29.5) in breast milk, 3.1 μg/L (0.2–22.4) in maternal urine, and 4.7 μg/L (0.3–25.3) in infant urine. There were no correlations between infant TSH or FT4 and iodine, perchlorate, and thiocyanate levels in breast milk, maternal urine, and infant urine. In multivariable analyses, perchlorate and thiocyanate levels in breast milk, maternal urine, and infant urine were not significant predictors of infant TSH or FT4. Conclusions Boston-area mothers and their breastfed infants are generally iodine sufficient. Although environmental perchlorate and thiocyanate

  16. Spectrophotometric determination of molybdenum in rocks with thiocyanate

    USGS Publications Warehouse

    Lillie, E.G.; Greenland, L.P.

    1974-01-01

    A rapid procedure for the determination of microgram amounts of molybdenum in rocks is described. After acid decomposition, molybdenum is extracted from a hydrochloric acid solution into xylene with tributyl phosphate. After back-extraction with water, molybdenum is extracted as the ??-benzoinoximate into chloroform, stripped into hydrochloric acid extracted as the thiocyanate into amyl alcohol, and determined spectrophotometrically. The molybdenum thiocyanate color produced is stable, sensitive, and reproducible. Results of analyses of several of the U.S. Geological Survey standard rocks are given. ?? 1974.

  17. Development of a PBPK model of thiocyanate in rats with an extrapolation to humans: A computational study to quantify the mechanism of action of thiocyanate kinetics in thyroid.

    PubMed

    Willemin, Marie-Emilie; Lumen, Annie

    2016-09-15

    Thyroid homeostasis can be disturbed due to thiocyanate exposure from the diet or tobacco smoke. Thiocyanate inhibits both thyroidal uptake of iodide, via the sodium-iodide symporter (NIS), and thyroid hormone (TH) synthesis in the thyroid, via thyroid peroxidase (TPO), but the mode of action of thiocyanate is poorly quantified in the literature. The characterization of the link between intra-thyroidal thiocyanate concentrations and dose of exposure is crucial for assessing the risk of thyroid perturbations due to thiocyanate exposure. We developed a PBPK model for thiocyanate that describes its kinetics in the whole-body up to daily doses of 0.15mmol/kg, with a mechanistic description of the thyroidal kinetics including NIS, passive diffusion, and TPO. The model was calibrated in a Bayesian framework using published studies in rats. Goodness-of-fit was satisfactory, especially for intra-thyroidal thiocyanate concentrations. Thiocyanate kinetic processes were quantified in vivo, including the metabolic clearance by TPO. The passive diffusion rate was found to be greater than NIS-mediated uptake rate. The model captured the dose-dependent kinetics of thiocyanate after acute and chronic exposures. Model behavior was evaluated using a Morris screening test. The distribution of thiocyanate into the thyroid was found to be determined primarily by the partition coefficient, followed by NIS and passive diffusion; the impact of the latter two mechanisms appears to increase at very low doses. Extrapolation to humans resulted in good predictions of thiocyanate kinetics during chronic exposure. The developed PBPK model can be used in risk assessment to quantify dose-response effects of thiocyanate on TH. PMID:27445130

  18. Coordination Chemistry of Homoleptic Actinide(IV)-Thiocyanate Complexes.

    PubMed

    Carter, Tyler J; Wilson, Richard E

    2015-10-26

    The synthesis, X-ray crystal structure, vibrational and optical spectroscopy for the eight-coordinate thiocyanate compounds, [Et4 N]4 [Pu(IV) (NCS)8 ], [Et4 N]4 [Th(IV) (NCS)8 ], and [Et4 N]4 [Ce(III) (NCS)7 (H2 O)] are reported. Thiocyanate was found to rapidly reduce plutonium to Pu(III) in acidic solutions (pH<1) in the presence of NCS(-) . The optical spectrum of [Et4 N][SCN] containing Pu(III) solution was indistinguishable from that of aquated Pu(III) suggesting that inner-sphere complexation with [Et4 N][SCN] does not occur in water. However, upon concentration, the homoleptic thiocyanate complex [Et4 N]4 [Pu(IV) (NCS)8 ] was crystallized when a large excess of [Et4 N][NCS] was present. This compound, along with its U(IV) analogue, maintains inner-sphere thiocyanate coordination in acetonitrile based on the observation of intense ligand-to-metal charge-transfer bands. Spectroscopic and crystallographic data do not support the interaction of the metal orbitals with the ligand π system, but support an enhanced An(IV) -NCS interaction, as the Lewis acidity of the metal ion increases from Th to Pu.

  19. Accelerated corrosion of stainless steel in thiocyanate-containing solutions

    SciTech Connect

    Pistorius, P Chris; Li, Wen

    2012-09-19

    It is known that reduced sulfur compounds (such as thiocyanate and thiosulfate) can accelerate active corrosion of austenitic stainless steel in acid solutions, but before we started this project the mechanism of acceleration was largely unclear. This work combined electrochemical measurements and analysis using scanning electron microscopy (SEM) and X-ray photo-electron spectroscopy (XPS), which provided a comprehensive understanding of the catalytic effect of reduced sulfur species on the active corrosion of stainless steel. Both the behavior of the pure elements and the steel were studied and the work focused on the interaction between the pure elements of the steel, which is the least understood area. Upon completion of this work, several aspects are now much clearer. The main results from this work can be summarized as follows: The presence of low concentrations (around 0.1 mM) of thiocyanate or tetrathionate in dilute sulfuric acid greatly accelerates the anodic dissolution of chromium and nickel, but has an even stronger effect on stainless steels (iron-chromium-nickel alloys). Electrochemical measurements and surface analyses are in agreement with the suggestion that accelerated dissolution really results from suppressed passivation. Even well below the passivation potential, the electrochemical signature of passivation is evident in the electrode impedance; the electrode impedance shows clearly that this pre-passivation is suppressed in the presence of thiocyanate. For the stainless steels, remarkable changes in the morphology of the corroded metal surface and in the surface concentration of chromium support the suggestion that pre-passivation of stainless steels is suppressed because dissolution of chromium is accelerated. Surface analysis confirmed that adsorbed sulfur / sulfide forms on the metal surfaces upon exposure to solutions containing thiocyanate or thiosulfate. For pure nickel, and steels containing nickel (and residual copper), bulk sulfide

  20. Determining diffusion coefficients of ionic liquids by means of field cycling nuclear magnetic resonance relaxometry

    NASA Astrophysics Data System (ADS)

    Kruk, D.; Meier, R.; Rachocki, A.; Korpała, A.; Singh, R. K.; Rössler, E. A.

    2014-06-01

    Field Cycling Nuclear Magnetic Resonance (FC NMR) relaxation studies are reported for three ionic liquids: 1-ethyl-3- methylimidazolium thiocyanate (EMIM-SCN, 220-258 K), 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM-BF4, 243-318 K), and 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM-PF6, 258-323 K). The dispersion of 1H spin-lattice relaxation rate R1(ω) is measured in the frequency range of 10 kHz-20 MHz, and the studies are complemented by 19F spin-lattice relaxation measurements on BMIM-PF6 in the corresponding frequency range. From the 1H relaxation results self-diffusion coefficients for the cation in EMIM-SCN, BMIM-BF4, and BMIM-PF6 are determined. This is done by performing an analysis considering all relevant intra- and intermolecular relaxation contributions to the 1H spin-lattice relaxation as well as by benefiting from the universal low-frequency dispersion law characteristic of Fickian diffusion which yields, at low frequencies, a linear dependence of R1 on square root of frequency. From the 19F relaxation both anion and cation diffusion coefficients are determined for BMIM-PF6. The diffusion coefficients obtained from FC NMR relaxometry are in good agreement with results reported from pulsed- field-gradient NMR. This shows that NMR relaxometry can be considered as an alternative route of determining diffusion coefficients of both cations and anions in ionic liquids.

  1. Determining diffusion coefficients of ionic liquids by means of field cycling nuclear magnetic resonance relaxometry.

    PubMed

    Kruk, D; Meier, R; Rachocki, A; Korpała, A; Singh, R K; Rössler, E A

    2014-06-28

    Field Cycling Nuclear Magnetic Resonance (FC NMR) relaxation studies are reported for three ionic liquids: 1-ethyl-3- methylimidazolium thiocyanate (EMIM-SCN, 220-258 K), 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM-BF4, 243-318 K), and 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM-PF6, 258-323 K). The dispersion of (1)H spin-lattice relaxation rate R1(ω) is measured in the frequency range of 10 kHz-20 MHz, and the studies are complemented by (19)F spin-lattice relaxation measurements on BMIM-PF6 in the corresponding frequency range. From the (1)H relaxation results self-diffusion coefficients for the cation in EMIM-SCN, BMIM-BF4, and BMIM-PF6 are determined. This is done by performing an analysis considering all relevant intra- and intermolecular relaxation contributions to the (1)H spin-lattice relaxation as well as by benefiting from the universal low-frequency dispersion law characteristic of Fickian diffusion which yields, at low frequencies, a linear dependence of R1 on square root of frequency. From the (19)F relaxation both anion and cation diffusion coefficients are determined for BMIM-PF6. The diffusion coefficients obtained from FC NMR relaxometry are in good agreement with results reported from pulsed- field-gradient NMR. This shows that NMR relaxometry can be considered as an alternative route of determining diffusion coefficients of both cations and anions in ionic liquids.

  2. Thiocyanation of BODIPY dyes and their conversion to thioalkylated derivatives.

    PubMed

    de Rezende, Lucas Cunha Dias; de Melo, Shaiani Maria Gil; Boodts, Stijn; Verbelen, Bram; Dehaen, Wim; da Silva Emery, Flavio

    2015-06-01

    A high-yielding method for the direct thiocyanation of BODIPY dyes is described. In 1,3-dimethyl BODIPYs, the thiocyanato group adds at position 2, whereas the insertion occurs at position 5 in 3-amino BODIPYs. The transformation of the thiocyanato group enables the synthesis of thioalkylated BODIPYs. 2-Thioalkylated BODIPYs and 3-thiocyanato-5-piperidino BODIPYs exhibit interesting spectroscopical features. Hence, the described synthetic methodology can be used for the photophysical tuning of BODIPY dyes. PMID:25946645

  3. Recent advances in the chemistry of organic thiocyanates.

    PubMed

    Castanheiro, Thomas; Suffert, Jean; Donnard, Morgan; Gulea, Mihaela

    2016-02-01

    Organic thiocyanates are important synthetic intermediates to access valuable sulfur-containing compounds. In this review the different methods for their preparation and their synthetic applications will be presented. The literature of the last 15 years will be covered, highlighting selected recent advances in the chemistry of this class of compounds. We hope to offer chemists the tools to have a good grasp of this singular functionality and open the door to further progress in this chemistry.

  4. Investigation of concentration of thiocyanate ion in raw cow's milk from China, New Zealand and the Netherlands.

    PubMed

    Yong, Ling; Wang, Yibaina; Yang, Dajin; Liu, Zhaoping; Abernethy, Grant; Li, Jianwen

    2017-01-15

    Thiocyanate ion is a natural component of cow's milk (hereinafter as milk) which may be artificially augmented to activate the lactoperoxidase milk preservation system. This study presents a survey of thiocyanate levels in raw milk and proposes a naturally occurring baseline concentration of thiocyanate in milk, which is the basis for market supervision. 1669 raw milk samples from China, 270 samples from New Zealand and 120 from the Netherlands were collected in the survey. 65% of the samples contained thiocyanate above the detection limit. The average concentration of thiocyanate was 2.11mg/kg (0.10-16.20mg/kg). Differences in the concentrations of thiocyanate were found among three countries, the 12 selected provinces in China, and between summer and winter. The baseline concentration of thiocyanate found in raw cow's milk was statistically calculated and rounded to 9.0mg/kg. Thiocyanate in milk at this level does not present a food safety concern.

  5. Investigation of concentration of thiocyanate ion in raw cow's milk from China, New Zealand and the Netherlands.

    PubMed

    Yong, Ling; Wang, Yibaina; Yang, Dajin; Liu, Zhaoping; Abernethy, Grant; Li, Jianwen

    2017-01-15

    Thiocyanate ion is a natural component of cow's milk (hereinafter as milk) which may be artificially augmented to activate the lactoperoxidase milk preservation system. This study presents a survey of thiocyanate levels in raw milk and proposes a naturally occurring baseline concentration of thiocyanate in milk, which is the basis for market supervision. 1669 raw milk samples from China, 270 samples from New Zealand and 120 from the Netherlands were collected in the survey. 65% of the samples contained thiocyanate above the detection limit. The average concentration of thiocyanate was 2.11mg/kg (0.10-16.20mg/kg). Differences in the concentrations of thiocyanate were found among three countries, the 12 selected provinces in China, and between summer and winter. The baseline concentration of thiocyanate found in raw cow's milk was statistically calculated and rounded to 9.0mg/kg. Thiocyanate in milk at this level does not present a food safety concern. PMID:27542450

  6. Infrared Spectroscopic Analysis of Linkage Isomerism in Metal-Thiocyanate Complexes

    ERIC Educational Resources Information Center

    Baer, Carl; Pike, Jay

    2010-01-01

    We developed an experiment suitable for an advanced inorganic chemistry laboratory that utilizes a cooperative learning environment, which allows students to develop an empirical method of determining the bonding mode of a series of unknown metal-thiocyanate complexes. Students synthesize the metal-thiocyanate complexes and obtain the FT-IR…

  7. Structural and mechanical studies of cadmium manganese thiocyanate crystal

    NASA Astrophysics Data System (ADS)

    Manikandan, M. R.; Vijayaprasath, G.; babu, G. Anandha; Bhagavannarayan, G.; Vijayan, N.; Ravi, G.

    2012-06-01

    Single crystals of cadmium manganese thiocyanate (CMTC) have been synthesized successfully and grown by slow evaporation method. The structural perfection of the grown crystals has been analyzed by High resolution X-ray diffraction (HRXRD), which shows the crystalline perfection of the grown crystal is quite good. Optical behavior was assessed by UV-Vis analysis and found that no absorption in the UV visible region and it may be useful for second harmonic applications. The mechanical hardness of the grown crystals was studied and Vicker's microhardness, Stiffness constant was calculated.

  8. Calculation of Vibrational Spectra for Coordinated Thiocyanate Ion in Acetonitrile

    NASA Astrophysics Data System (ADS)

    Mikhailov, G. P.

    2016-07-01

    The impact of the association of lithium cation with NCS- ion in acetonitrile on the vibrational spectrum was studied by the density-functional method in the B3LYP/6-31+G(d,p) approximation. The best agreement between experimental and calculated ionic association data was achieved taking into account the nonspecific solvation, oversolvation, and solubility of ionic complexes within the discrete-continuum model. The microstructures of the thiocyanate ion in a contact ion pair with lithium cation and ion-pair dimer and trimer in acetonitrile were established.

  9. Rotational dynamics of thiocyanate ions in highly concentrated aqueous solutions.

    PubMed

    Kim, Heejae; Park, Sungnam; Cho, Minhaeng

    2012-05-14

    The thiocyanate (SCN(-)) anion is known as one of the best denaturants, which is also capable of breaking the hydrogen-bond network of water and destabilizing native structures of proteins. Despite prolonged efforts to understand the underlying mechanism of such Hofmeister effects, detailed dynamics of the ions in a highly concentrated solution have not been fully elucidated yet. Here, we used a dispersive IR pump-probe spectroscopic method to study the dependence of vibrational lifetimes and rotational relaxation times of thiocyanate ions on KSCN concentration in D(2)O. The nitrile stretch mode is used as a vibrational probe for dispersed IR pump-probe and FTIR measurements. To avoid possible self-attenuation of the IR pump-probe signal by highly concentrated SCN(-) ions, we added a small amount of (13)C-isotope-labeled thiocyanate ions (S(13)CN(-)) and focused on the excited-state absorption contribution to the IR pump-probe signal of the (13)C-isotope-labeled nitrile stretch mode. Quite unexpectedly, the vibrational lifetime of S(13)CN(-) ions is independent of the total KSCN concentration in the range from 0.46 m (molality) to 11.8 m while the rotational relaxation time of S(13)CN(-) ions is linearly dependent on the total KSCN concentration. By combining the present experimental findings with the fact that the dissolved ions of KSCN salt have a strong tendency to form a large ion cluster in a highly concentrated aqueous solution, we believe that the ion clusters consisting of potassium and thiocyanate ion pairs in D(2)O behave like ionic liquids and the ions inside ion clusters are weakly bound by electrostatic Coulombic interactions. The ability of SCN(-) ions to form ion clusters in aqueous protein solutions seems to be a key to understand the Hofmeister ion effect. We anticipate that the present experimental results provide a clue for further elucidating the underlying mechanism of the Hofmeister ion effects on protein stability in the future. PMID:22407336

  10. Anion-exchange separations of metal ions in thiocyanate media.

    PubMed

    Fritz, J S; Kaminski, E E

    1971-05-01

    The analytical potential of a weak-base macroreticular anion-exchange resin for the quantitative separation of metal ions in thiocyanate media is investigated and demonstrated. Distribution data are given for the sorption of some 25 metal ions from aqueous mixtures of potassium thiocyanate (1.0M or less) and 0.5M hydrochloric acid. The magnitude of the distribution data suggests many possible separations, some of which were quantitatively performed by procedures which are fast, simple and require only mild conditions. Representative separations are removal of traces of iron(III) and copper(II) from water samples prior to the determination of water hardness (calcium and magnesium), separation of nickel(II) from vanadium(IV) and the separation of thorium(IV) from titanium(IV). Some multicomponent separations are the separation of rare earths(III) and thorium(IV) from scandium(III) and the separation of rare earths(III) from iron(III) and uranium(VI). PMID:18960914

  11. Thiocyanate and hydroxyl ions inactivate the scrapie agent.

    PubMed Central

    Prusiner, S B; Groth, D F; McKinley, M P; Cochran, S P; Bowman, K A; Kasper, K C

    1981-01-01

    To probe the macromolecular structure of the scrapie agent and explore conditions for monomerization, the stability of the agent in low concentrations of inorganic ions was determined. A reduction by a factor of 10(5) in scrapie titer was found on exposure of the agent to 1 M KSCN or 0.3 M NaOH. In addition to the inactivation by thiocyanate ions, other chaotropic ions such as guanidinium and trichloroacetate inactivate the scrapie agent. Removal of thiocyanate ions by dialysis or glass permeation chromatography prevented the reduction in scrapie agent infectivity. Addition of equimolar amounts of (NH4)2SO4, a nonchaotrope, to preparations containing 1 M KSCN also prevented the loss of scrapie infectivity. In contrast, neutralization of the alkali-treated fractions with HCl did not restore infectivity. Acidification of partially purified fractions did not cause inactivation of the agent but did result in precipitation of the infectious agent. Inactivation by relatively low concentrations of chaotropic ions is consistent with many observations, all of which suggest that the scrapie agent contains a protein component that is essential for the maintenance of infectivity. Thus, it is unlikely that the agent is composed only of a "naked" nucleic acid. Certainly, if the agent were a naked nucleic acid, its lability in alkali virtually eliminates the possibility that it is composed of a single-stranded molecule of DNA. PMID:6794034

  12. Preparation of molecule-based magnets from metal thiocyanate complexes

    NASA Astrophysics Data System (ADS)

    Shurdha, Endrit

    2011-07-01

    The study of magnetism has enabled many technological applications that are ubiquitous in our daily life. Presently, most of the magnetic applications use metal/metal oxide magnets, which are readily available. In the last few decades, research has focused on a new class of magnetic materials, molecule-based magnets. This class of materials has diverse physical and chemical properties, which can be controlled by synthetic methods. Utilizing a variety of metals and ligands, researchers can control and fine tune various aspects of these magnetic materials, such as structural connections and possibly magnetic properties. Tetracyanoethylene (TCNE) is widely used in the preparation of molecule-based magnets due to its unique electronic and connectivity properties. TCNE has multiple binding sites, which gives it a diverse range of structural connectivity. Also, TCNE can be reduced easily to form a radical anion, which facilitates spin communication between metal centers allowing isolation of magnetically ordered systems such as V(TCNE)2 (a room temperature molecule-based magnet). M-TCNE magnets are prepared from solvated MII complexes or a metal carbonyl and TCNE in dichloromethane. The reaction involves the oxidation of the MII to MIII and the reduction of TCNE. More coordinating solvents used to prepare TCNE molecule-based magnets facilitate the dimerization of the radical TCNE, which does not allow for long-range ordering. The work presented herein will show the synthesis of MII thiocyanate complexes and their reaction with TCNE radical anion to yield M(TCNE)[C4(CN)8]1/2, which is obtained through ligand substitution between TCNE and thiocyanate. The development of new MII thiocyanate complexes through MII(NCMe)x(BF4)2 (x = 4, 6) in acetone, acetonitrile, and tetrahydrofuran will be the focus of Chapter 2. Also, in Chapter 2, structural and magnetic characterization will be discussed. Few of the metal thiocyanate complexes exhibit antiferromagnetic ordering at

  13. [Salivary, urinary and plasma thiocyanate in smokers and non-smokers].

    PubMed

    Ngogang, J; Eben-Moussi, E; Raisonnier, A

    1983-03-01

    Thiocyanate is a major metabolic product of hydrocyanic acid. Its concentration in the serum, urine and saliva of individuals with little exposure to hydrocyanic acid (i.e. non smokers) is very low. But about three fold higher concentrations of thiocyanate are found in the sera, urine and saliva of smokers as compared to non smokers, because of cyanide provided by cigarette smoke. The concentrations of thiocyanate in the three biological fluids studied were different and it appeared to be no correlation in the distribution of thiocyanate concentrations in these fluids when individual subjects were compared. Urinary and salivary concentration power showed decreased kidney excretion of thiocyanate in smokers. The appearance or the disappearance of thiocyanates in the saliva and the urine takes place slowly. The salivary or urinary levels of thiocyanates are therefore good indicators of chronic intoxication from tobacco because it is not very sensitive to daily variations in tobacco smoking; it reflects the slow transformation of cyanide as well as the final elimination of this ion from urine which is slowed down in smokers. PMID:6343971

  14. Factors influencing thiocyanate toxicity in rainbow trout Salmo gairdneri

    SciTech Connect

    Heming, T.A.; Blumhagen, K.A. )

    1989-09-01

    The toxicity of thiocyanate (SCN{sup {minus}}) to fish is influenced by the level of fish activity. This is evidenced most dramatically when fish are forced to perform short bouts of strenuous swimming, such as occurs during capture avoidance. Strenuous exercise of SCN{sup {minus}}-exposed fish results in sudden death syndrome, characterized by the immediate onset of convulsions, loss of equilibrium and buoyancy, flaring of the operculum, darkening of the skin epithelium and, within minutes, cessation of ventilation and extreme rigor. The present study was undertaken to examine the accumulation and toxicity of SCN{sup {minus}} in rainbow trout (Salmo gairdneri), in relation to exercise stress and ambient water quality. The effect of a single bout of exercise on blood SCN{sup {minus}} concentration was measured. In addition, effects of water hardness and Cl{sup {minus}} concentration on the accumulation of SCN{sup {minus}} in blood were determined.

  15. Uric acid and thiocyanate as competing substrates of lactoperoxidase.

    PubMed

    Seidel, Antonia; Parker, Heather; Turner, Rufus; Dickerhof, Nina; Khalilova, Irada S; Wilbanks, Sigurd M; Kettle, Anthony J; Jameson, Guy N L

    2014-08-01

    The physiological function of urate is poorly understood. It may act as a danger signal, an antioxidant, or a substrate for heme peroxidases. Whether it reacts sufficiently rapidly with lactoperoxidase (LPO) to act as a physiological substrate remains unknown. LPO is a mammalian peroxidase that plays a key role in the innate immune defense by oxidizing thiocyanate to the bactericidal and fungicidal agent hypothiocyanite. We now demonstrate that urate is a good substrate for bovine LPO. Urate was oxidized by LPO to produce the electrophilic intermediates dehydrourate and 5-hydroxyisourate, which decayed to allantoin. In the presence of superoxide, high yields of hydroperoxides were formed by LPO and urate. Using stopped-flow spectroscopy, we determined rate constants for the reaction of urate with compound I (k1 = 1.1 × 10(7) M(-1) s(-1)) and compound II (k2 = 8.5 × 10(3) M(-1) s(-1)). During urate oxidation, LPO was diverted from its peroxidase cycle because hydrogen peroxide reacted with compound II to give compound III. At physiologically relevant concentrations, urate competed effectively with thiocyanate, the main substrate of LPO for oxidation, and inhibited production of hypothiocyanite. Similarly, hypothiocyanite-dependent killing of Pseudomonas aeruginosa was inhibited by urate. Allantoin was present in human saliva and associated with the concentration of LPO. When hydrogen peroxide was added to saliva, oxidation of urate was dependent on its concentration and peroxidase activity. Our findings establish urate as a likely physiological substrate for LPO that will influence host defense and give rise to reactive electrophilic metabolites.

  16. Uric Acid and Thiocyanate as Competing Substrates of Lactoperoxidase*

    PubMed Central

    Seidel, Antonia; Parker, Heather; Turner, Rufus; Dickerhof, Nina; Khalilova, Irada S.; Wilbanks, Sigurd M.; Kettle, Anthony J.; Jameson, Guy N. L.

    2014-01-01

    The physiological function of urate is poorly understood. It may act as a danger signal, an antioxidant, or a substrate for heme peroxidases. Whether it reacts sufficiently rapidly with lactoperoxidase (LPO) to act as a physiological substrate remains unknown. LPO is a mammalian peroxidase that plays a key role in the innate immune defense by oxidizing thiocyanate to the bactericidal and fungicidal agent hypothiocyanite. We now demonstrate that urate is a good substrate for bovine LPO. Urate was oxidized by LPO to produce the electrophilic intermediates dehydrourate and 5-hydroxyisourate, which decayed to allantoin. In the presence of superoxide, high yields of hydroperoxides were formed by LPO and urate. Using stopped-flow spectroscopy, we determined rate constants for the reaction of urate with compound I (k1 = 1.1 × 107 m−1 s−1) and compound II (k2 = 8.5 × 103 m−1 s−1). During urate oxidation, LPO was diverted from its peroxidase cycle because hydrogen peroxide reacted with compound II to give compound III. At physiologically relevant concentrations, urate competed effectively with thiocyanate, the main substrate of LPO for oxidation, and inhibited production of hypothiocyanite. Similarly, hypothiocyanite-dependent killing of Pseudomonas aeruginosa was inhibited by urate. Allantoin was present in human saliva and associated with the concentration of LPO. When hydrogen peroxide was added to saliva, oxidation of urate was dependent on its concentration and peroxidase activity. Our findings establish urate as a likely physiological substrate for LPO that will influence host defense and give rise to reactive electrophilic metabolites. PMID:24928513

  17. Biodegradation of thiocyanate in mining-contaminated groundwater

    NASA Astrophysics Data System (ADS)

    Spurr, L. P.; Watts, M. P.; Moreau, J. W.

    2015-12-01

    In-situ SCN- biodegradation as a strategy for remediating contaminated groundwater remains largely unproven. This study aimed to culture and characterise a community of SCN--degrading microbes from mining-contaminated groundwater, and to optimize the efficiency of this process under varied geochemical conditions. A gold ore processing plant in Victoria, Australia, has generated high amounts of thiocyanate (SCN-)-contaminated waste effluent. This effluent collects in a tailings storage facility (TSF) on site and seepage has contaminated local groundwater. This SCN- plume recently escaped the mine lease in a plume flowing partly through a confined aquifer and partly along buried paleochannel gravels. Groundwater samples were collected using a low-flow pump from two bores near the TSF. The pH of the SCN- contaminated groundwater typically varies between 4 and 6, and dissolved O2 varies between 1 and 40 ppm. SCN- concentrations in off-lease groundwater have increased from 10 ppm in 2010 to over 150 ppm in 2015. Cultures were inoculated directly from the groundwater, and filtered groundwater was used with amendments as the basal growth medium Cultures were subjected to geochemical amendments including changes in dissolved O2, pH, SCN- concentration and additions of organic carbon, phosphate or both. The enriched microbial consortia could not degrade thiocyanate under anoxic conditions, but some could completely degrade high concentrations of SCN- (>800mg L-1) under oxic conditions. Biodegradation accelerated with the addition of phosphate, while the addition of organic carbon actually limited the rate. SCN- degrading cultures are undergoing DNA sequencing for species identification and comparison to SCN--degrading cultures inoculated from surface waters in the TSF.

  18. 76 FR 22904 - Ferm Solutions, Inc.; Filing of Food Additive Petition (Animal Use); Erythromycin Thiocyanate

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-04-25

    ... thiocyanate as an antimicrobial processing aid in fuel-ethanol fermentations with respect to its consequent... processing aid in fuel-ethanol fermentations with respect to its ] consequent presence in byproduct...

  19. Oxidative nucleophilic strategy for synthesis of thiocyanates and trifluoromethyl sulfides from thiols.

    PubMed

    Yamaguchi, Kazuya; Sakagami, Konomi; Miyamoto, Yumi; Jin, Xiongjie; Mizuno, Noritaka

    2014-12-01

    Thiocyanates and trifluoromethyl sulfides are important compounds and have classically been synthesized via multistep procedures together with the formation of significant amounts of byproducts. Herein, we demonstrate an oxidative nucleophilic strategy for the synthesis of thiocyanates and trifluoromethyl sulfides from thiol starting materials using nucleophilic reagents such as TMSCN and TMSCF3 (TMS = trimethylsilyl). In the presence of a 2 × 2 manganese oxide-based octahedral molecular sieve (OMS-2) and potassium fluoride (KF), various structurally diverse thiocyanates and trifluoromethyl sulfides could be synthesized in almost quantitative yields (typically >90%). The presented cyanation and trifluoromethylation reactions proceed through the OMS-2-catalyzed oxidative homocoupling of thiols to give disulfides followed by nucleophilic bond cleavage to produce the desired compounds and thiolate species (herein S-trimethylsilylated thiols). OMS-2 can catalyze oxidative homocoupling of the thiolate species, thus resulting formally in the quantitative production of thiocyanates and trifluoromethyl sulfides from thiols. PMID:25297894

  20. Unique stress response to the lactoperoxidase-thiocyanate enzyme system in Escherichia coli.

    PubMed

    Sermon, Jan; Vanoirbeek, Kristof; De Spiegeleer, Philipp; Van Houdt, Rob; Aertsen, Abram; Michiels, Chris W

    2005-03-01

    Using a differential fluorescence induction approach, we screened a promoter trap library constructed in a vector with a promoterless gfp gene for Escherichia coli MG1655 promoters that are induced upon challenge with the antimicrobial lactoperoxidase-thiocyanate enzyme system. None of the thirteen identified lactoperoxidase-inducible open reading frames was inducible by H(2)O(2) or by the superoxide generator plumbagin. However, analysis of specific promoters of known stress genes showed some of these, including recA, dnaK and sodA, to be inducible by the lactoperoxidase-thiocyanate enzyme system. The results show that the lactoperoxidase-thiocyanate enzyme system elicits a distinct stress response different from but partly overlapping other oxidative stress responses. Several of the induced genes or pathways may be involved in bacterial defense against the toxic effects of the lactoperoxidase-thiocyanate enzyme system.

  1. New insights into the genetic and metabolic diversity of thiocyanate-degrading microbial consortia.

    PubMed

    Watts, Mathew P; Moreau, John W

    2016-02-01

    Thiocyanate is a common contaminant of the gold mining and coal coking industries for which biological degradation generally represents the most viable approach to remediation. Recent studies of thiocyanate-degrading bioreactor systems have revealed new information on the structure and metabolic activity of thiocyanate-degrading microbial consortia. Previous knowledge was limited primarily to pure-culture or co-culture studies in which the effects of linked carbon, sulfur and nitrogen cycling could not be fully understood. High throughput sequencing, DNA fingerprinting and targeted gene amplification have now elucidated the genetic and metabolic diversity of these complex microbial consortia. Specifically, this has highlighted the roles of key consortium members involved in sulfur oxidation and nitrification. New insights into the biogeochemical cycling of sulfur and nitrogen in bioreactor systems allow tailoring of the microbial metabolism towards meeting effluent composition requirements. Here we review these rapidly advancing studies and synthesize a conceptual model to inform new biotechnologies for thiocyanate remediation. PMID:26596573

  2. Microalgae-mediated simultaneous treatment of toxic thiocyanate and production of biodiesel.

    PubMed

    Ryu, Byung-Gon; Kim, Jungmin; Yoo, Gursong; Lim, Jun-Taek; Kim, Woong; Han, Jong-In; Yang, Ji-Won

    2014-04-01

    In this work, a method for simultaneously degrading the toxic pollutant, thiocyanate, and producing microalgal lipids using mixed microbial communities was developed. Aerobic activated sludge was used as the seed culture and thiocyanate was used as the sole nitrogen source. Two cultivation methods were sequentially employed: a lithoautotrophic mode and a photoautotrophic mode. Thiocyanate hydrolysis and a nitrification was found to occur under the first (lithoautotrophic) condition, while the oxidized forms of nitrogen were assimilated by the photoautotrophic consortium and lipids were produced under the second condition. The final culture exhibited good settling efficiency (∼ 70% settling over 10 min), which can benefit downstream processing. The highest CO2 fixation rate and lipid productivity were observed with 2.5% and 5% CO2, respectively. The proposed integrated algal-bacterial system appears to be a feasible and even beneficial option for thiocyanate treatment and production of microbial lipids. PMID:24603489

  3. Aqueous ammonium thiocyanate solutions as refractive index-matching fluids with low density and viscosity

    NASA Astrophysics Data System (ADS)

    Borrero-Echeverry, D.; Morrison, B. C. A.

    2016-07-01

    We show that aqueous solutions of ammonium thiocyanate ({NH}4{SCN}) can be used to match the index of refraction of several transparent materials commonly used in experiments, while maintaining low viscosity and density compared to other common refractive index-matching liquids. We present empirical models for estimating the index of refraction, density, and kinematic viscosity of these solutions as a function of temperature and concentration. Finally, we summarize the chemical compatibility of ammonium thiocyanate with materials commonly used in apparatus.

  4. A mild copper-catalyzed aerobic oxidative thiocyanation of arylboronic acids with TMSNCS.

    PubMed

    Sun, Nan; Che, Liusheng; Mo, Weimin; Hu, Baoxiang; Shen, Zhenlu; Hu, Xinquan

    2015-01-21

    A facile and efficient transformation of arylboronic acids to their corresponding aryl thiocyanates has been successfully developed. Based on the CuCl-catalyzed oxidative cross-coupling reaction between arylboronic acids and trimethylsilylisothiocyanate (TMSNCS) under oxygen atmosphere, the transformation can be readily conducted at ambient temperature. The newly-developed protocol provided a competitive synthetic approach to aryl thiocyanates that can tolerate a broad range of reactive functional groups and/or strong electron-withdrawing groups. PMID:25514847

  5. Technology for processing ammonium rhodanide of coking plants into high-purity ammonium thiocyanate and thiourea

    SciTech Connect

    Urakaev, F.K.

    2009-04-15

    The regularities of the reversible reaction of isomerization of ammonium thiocyanate (NH{sub 4}NCS) into thiourea (NH{sub 2}){sub 2}CS, and the reverse reaction, were analyzed. An ecologically clean and highly efficient method for the extraction, purification, separation, and production of isomers from the coal byproduct ammonium thiocyanate was developed based on the measured volatilities of NH{sub 4}NCS and (NH{sub 2}){sub 2}CS.

  6. Cyanide conversion to thiocyanate by 3-mercaptopyruvate sulfurtransferase (MPST)

    SciTech Connect

    Baskin, S.I.; Wing, D.A.; Kirby, S.D.

    1990-02-26

    Cyanide (CN) metabolism by MPST may detoxify CN to its less harmful product thiocyanate (SCN). In addition, MPST displays greater activity than rhodanese in extramitochondrial sites and in other organs which may play an important role in CN's toxicity. A 3% (W/V) homogenate of bovine kidney MPST was prepared. It was assayed using CN and mercaptopyruvate. The buffered (pH 9.5) suspension was incubated for 10 minutes. The reaction was stopped with 38% formaldehyde containing 20% ferric nitrate in nitric acid and measured at 460 nm. Phosphate buffer decreased the apparent rate of conversion of CN to SCN by 90% compared with glycine, borate, or bistris propane buffers. Hypotaurine and propanethiosulfate, but not taurine or thiomallic acid, increased the activity of MPST in a dose-related manner; e.g., hypotaurine, 0.1, 1 and 10 mmole, increased MPST indicates that several compounds increase the rate of formation of SCN from CN and may provide a potential new class of antidotes against the toxicity of CN.

  7. [Radiolysis of aqueous solution of thiocyanate by gamma-rays].

    PubMed

    Feng, Hai-bing; Yang, Ming-de; Hu, Hu-sheng; Huang, Hui-ping

    2008-06-01

    Radiolysis of aqueous solution of thiocyanate by 60Co gamma-rays was studied. In condition of pH = 1 and pH = 3,25 mg/L SCN- was decomposed under the dose of 6 kGy, with decomposition rate of 98.11% (pH = 1) and 95.97% (pH = 3) respectively. 25 mg/L SCN- (pH = 7) was decomposed under the dose of 9 kGy and the decomposition rate is 99.33%. In the alkaline condition, pH = 10 and pH = 12, the dose of 18 kGy was need, and the decomposition rate is 99.64% and 99.93% respectively. High SCN- concentration means that more radiation dose is need. From the comparison of before radiolysis and after radiolysis's TOC (total organic carbon) and TN (total nitrogen) of SCN- solution, little TOC and TN was removed. The determination of SO4(2-) and NO3- concentration indicated that sulfur element was removed and converted to SO4(2-), and nitrogen element rarely converted to NO3-, but converted to other forms of nitrogen.

  8. DETECTION OF A NEW INTERSTELLAR MOLECULE: THIOCYANIC ACID HSCN

    SciTech Connect

    Halfen, D. T.; Ziurys, L. M.; Bruenken, S.; Gottlieb, C. A.; McCarthy, M. C.; Thaddeus, P. E-mail: lziurys@as.arizona.edu E-mail: cgottlieb@cfa.harvard.edu E-mail: pthaddeus@cfa.harvard.edu

    2009-09-10

    A new interstellar molecule, HSCN (thiocyanic acid), an energetic isomer of the well-known species HNCS, has been detected toward Sgr B2(N) with the Arizona Radio Observatory 12 m telescope. Eight rotational transitions in the K{sub a} = 0 ladder were observed in the 2 mm and 3 mm bands. Five consecutive transitions in the 3 mm band are unblended, but three in the 2 mm band are partially masked by lines of other molecules. The peak intensity of all eight transitions are well described by a rotational temperature that is in very good agreement with that of many other molecules in this source. The line width and radial velocity of HSCN match closely with those of the ground state isomer HNCS (isothiocyanic acid), HNCO (isocyanic acid), and HOCN (cyanic acid); preliminary maps indicate that all four molecules are similarly distributed in Sgr B2. Although HSCN is calculated to lie over 3000 K higher in energy than HNCS, its column density of 1.3 x 10{sup 13} cm{sup -2} in Sgr B2(N) is only three times lower than that of HNCS. The fractional abundances of HSCN and HNCS relative to H{sub 2} are 4.5 x 10{sup -12} and 1.1 x 10{sup -11}. By analogy with the isomeric pair HCN and HNC, these two sulfur-bearing isomers are plausibly formed from a common cation precursor.

  9. Determination of trace amounts of thiocyanate by a new kinetic procedure based on an induction period

    NASA Astrophysics Data System (ADS)

    Chamjangali, M. Arab; Bagherian, G.; Salek-Gilani, N.

    2007-08-01

    A new, simple and sensitive kinetic spectrophotometric method with no need for removing of interfering substances is proposed for the determination of thiocyanate ion in biological and water samples. The procedure is based on the inhibiting effect of thiocyanate on the sodium periodate-potassium bromide-meta cresol purple (MCP) system in acidic media. The induction period of the reaction is proportional to the SCN - concentration. The decolorization of meta cresol purple by the reaction products was used to monitor the reaction spectrophotometrically at 525 nm. Under optimum conditions, thiocyanate can be determined in the range of 0.02-0.8 μg ml -1 with a 3 σ detection limit of 5 ng ml -1. The relative standard deviations for 10 replicate determinations of 0.060, 0.10 and 0.50 μg ml -1 thiocyanate are 3.7, 2.4 and 1.0%, respectively. This method has been successfully used to the determination of thiocyanate content in smokers and non-smokers saliva and spiked water sample.

  10. [Determination of iodide, thiocyanate and perchlorate ions in environmental water by two-dimensional ion chromatography].

    PubMed

    Lin, Li; Wang, Haibo; Shi, Yali

    2013-03-01

    A procedure for the determination of iodide, thiocyanate and perchlorate ions in environmental water by two-dimensional ion chromatography has been developed. At first the iodide, thiocyanate and perchlorate ions were separated from interfering ions by a column (IonPac AS16, 250 mm x 4 mm). The iodide ion, thiocyanate and perchlorate ions were then enriched with an enrichment column (MAC-200, 80 mm x 0.75 mm). In the 2nd-dimensional chromatography, iodide thiocyanate and perchlorate ions were separated and quantified by a capillary column (IonPac AS20 Capillary, 250 mm x 0.4 mm). The linear ranges were 0.05 -100 pg/L with correlation coefficients of 0. 999 9, and the detection limits were 0. 02 - 0.05 micro gg/L. The spiked recoveries of iodide, thiocyanate and perchlorate ions were in the range of 85.1% to 100.1%. The relative standard deviations of the recoveries were 1.7% to 4.9%.

  11. Bio-oxidation of thiocyanates typical of coal conversion effluents. Final report

    SciTech Connect

    Neufeld, R. D.; Mattson, L.; Lubon, P.

    1981-01-08

    Thiocyanates have been found in most coal conversion and coke plant effluents. The objectives of this study were to develop data for the biological degradation fate kinetics of thiocyanate removal, and to develop material balance information for the fate of sulfur and nitrogen resulting from such bio-decomposition of aqueous thiocyanates. A literature review of thiocyanate bio-degradation indicates that while much biochemistry information is available, little information in the biological processing arena is known. Based on both batch and continuous culture experiments utilizing an activated sludge type of system with strictly thiocyanate degradating organisms, the specific utilization rate for SCN degradation was found to follow a substrate inhibition biokinetic relationship as: d(SCN)/dt-X = 2.24/(1 + (5/SCN) + (SCN/1340)/sup 6/) where; d(SCN)/dt-X = lb SCN used/lb biomass-day, SCN = mg/L SCN in effluent. The observed biomass sludge production rate was quantified as a function of sludge age in the bio-reactor. The major metabolic by-products of SCN aerobic biodegradation are ammonia and sulfate, with such formation being stochiometric with SCN. High levels of SCN in coal conversion and Stretford system effluents may lead to biological nitrification process requirements to be added to the wastetreatment scheme for compliance with BAT effluent ammonia discharge restrictions.

  12. Simultaneous oxidation of cyanide and thiocyanate at high pressure and temperature.

    PubMed

    Oulego, Paula; Collado, Sergio; Laca, Adriana; Díaz, Mario

    2014-09-15

    Thiocyanate and cyanide are important contaminants that frequently appear mixed in industrial effluents. In this work the wet oxidation of mixtures of both compounds, simulating real compositions, was carried out in a semi-batch reactor at temperature between 393 K and 483 K and pressure in the range of 2.0-8.0 MPa. The presence of cyanide (3.85 mM) increased the kinetic constant of thiocyanate degradation by a factor of 1.6, in comparison to the value obtained for the individual degradation of thiocyanate, (5.95 ± 0.05) × 10(-5)s(-1). On the other hand, the addition of thiocyanate (0.98 mM) decreased the degradation rate of cyanide by 16%. This revealed the existence of synergistic and inhibitory phenomena between these two species. Additionally, cyanide was identified as an intermediate in the oxidation of thiocyanate, and formate, ammonia and sulfate were found to be the main reaction products. Taking into account the experimental data, a reaction pathway for the simultaneous wet oxidation of both pollutants was proposed. Two parallel reactions beginning from cyanate as intermediate were considered, one yielding ammonia and formate and the other giving carbon dioxide and nitrogen as final products.

  13. Serum and tissue thiocyanate concentrations in growing pigs fed cassava peel or corn based diets containing graded protein levels.

    PubMed

    Tewe, O O

    1984-11-01

    Thiocyanate concentrations of serum, liver, kidney, spleen and longissimus dorsi were determined in 64 growing Large White x Landrace pigs offered 8 experimental isocaloric diets containing different levels of cassava peel and crude protein. Cassava peel increased serum thiocyanate on day 60 (P less than 0.01) and day 90 (P less than 0.01) of the trial, while the crude protein level increased it (P less than 0.05) on days 30 and 90, respectively. Interaction of the two factors was significant on day 30 (P less than 0.05) and day 90 (P less than 0.05). There was a correlation between cyanide intake and serum thiocyanate level. Coefficient of determination revealed that cyanide alone accounted for 28.5; 60.6 and 48.8% variation in serum thiocyanate on days 30, 60 and 90, respectively. Liver, spleen and longissimus dorsi thiocyanate were affected by dietary protein intake (P less than 0.05). Thiocyanate concentration was higher (P less than 0.05) on cassava peel diet. Generally, crude protein at 5% reduced organ and muscle thiocyanate concentrations. A diet containing 112.2-117.3 mg/kg hydrocyanic acid (HCN) affected serum but not organ and muscle thiocyanate in protein-sufficient diets. PMID:6506092

  14. Catalytic wet oxidation of thiocyanate with homogeneous copper(II) sulphate catalyst.

    PubMed

    Collado, Sergio; Laca, Adriana; Díaz, Mario

    2010-05-15

    The wet oxidation of thiocyanate has been investigated in a semi-batch reactor at temperatures between 423 and 473 K and pressures between 6.1 x 10(3) and 1.0 x 10(4)kPa in the presence of copper(II) sulphate as catalyst. The effects of copper concentration, initial thiocyanate concentration, pressure and temperature on the reaction rate were analyzed and the main products of reaction were identified. A kinetic model for the Cu-catalyzed reaction is here proposed, including temperature, oxygen concentration, and the reduction of Cu(2+) to Cu(+) that gives an accurate prediction of the oxidation process under the assayed conditions. A mechanistic model based on the formation of a transition complex between a copper cation and two thiocyanate anions has been proposed for the catalytic wet oxidation.

  15. Effect of thiocyanate levels in milk on thyroid function in iodine deficient subjects.

    PubMed

    Dahlberg, P A; Bergmark, A; Eltom, M; Björck, L; Claesson, O

    1985-05-01

    To utilize the antibacterial effect of the lactoperoxidase system to prevent bacterial spoilage of raw milk it is necessary to increase the thiocyanate concentration of the milk. Thiocyanate has, however, a potent antithyroid effect which is enhanced by iodine deficiency. In this study the thyroid function has been studied, before and after 4 weeks daily administration of 250 ml of such treated milk, in 55 goitrous subjects living in an endemic goiter region of western Sudan. The iodine content was 0.1 mg/l and the thiocyanate content was either 3.6 mg/l (n 19) or 19 mg/l (n 36) in the milk. At the start of the experiment all subjects were iodine deficient with a urinary excretion of 40-50 micrograms/g creatinine. After 4 weeks daily intake of 4.75 mg of thiocyanate by way of milk the serum thiocyanate level increased by approximately 1.7 mg/l. Both at the beginning and at the end of the experimental period the serum levels of thyroxine, triiodothyronine and TSH were in the normal range for all subjects. After 4 weeks the TSH levels had decreased significantly, (from 2.6 +/- 0.2 to 2.1 +/- 0.2 mU/l, p less than 0.001) probably as an effect of the supplementary intake of iodine. The thyroid hormone levels remained unchanged during the experimental period. In conclusion, the intake of milk with an iodine concentration of 0.1 mg/l and a thiocyanate concentration of 19 mg/l does not have a negative effect on the thyroid function in iodine deficient subjects.

  16. The thiocyanate anion is a primary driver of carbon dioxide capture by ionic liquids

    NASA Astrophysics Data System (ADS)

    Chaban, Vitaly

    2015-01-01

    Carbon dioxide, CO2, capture by room-temperature ionic liquids (RTILs) is a vivid research area featuring both accomplishments and frustrations. This work employs the PM7-MD method to simulate adsorption of CO2 by 1,3-dimethylimidazolium thiocyanate at 300 K. The obtained result evidences that the thiocyanate anion plays a key role in gas capture, whereas the impact of the 1,3-dimethylimidazolium cation is mediocre. Decomposition of the computed wave function on the individual molecular orbitals confirms that CO2-SCN binding extends beyond just expected electrostatic interactions in the ion-molecular system and involves partial sharing of valence orbitals.

  17. Reactions of Starch in Ionic Liquids

    Technology Transfer Automated Retrieval System (TEKTRAN)

    We found that starches are found to be soluble at 80 ºC in ionic liquids such as 1-butyl-3-methylimidazolium chloride (BMIMCl) and 1-butyl-3-methylimidazolium dicyanamide (BMIMdca) in concentration up to 10% (w/w). Higher concentrations of biopolymers in these novel solvents resulted in solutions w...

  18. Determining diffusion coefficients of ionic liquids by means of field cycling nuclear magnetic resonance relaxometry

    SciTech Connect

    Kruk, D.; Meier, R.; Rössler, E. A.; Rachocki, A.; Korpała, A.; Singh, R. K.

    2014-06-28

    Field Cycling Nuclear Magnetic Resonance (FC NMR) relaxation studies are reported for three ionic liquids: 1-ethyl-3- methylimidazolium thiocyanate (EMIM-SCN, 220–258 K), 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM-BF{sub 4}, 243–318 K), and 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM-PF{sub 6}, 258–323 K). The dispersion of {sup 1}H spin-lattice relaxation rate R{sub 1}(ω) is measured in the frequency range of 10 kHz–20 MHz, and the studies are complemented by {sup 19}F spin-lattice relaxation measurements on BMIM-PF{sub 6} in the corresponding frequency range. From the {sup 1}H relaxation results self-diffusion coefficients for the cation in EMIM-SCN, BMIM-BF{sub 4}, and BMIM-PF{sub 6} are determined. This is done by performing an analysis considering all relevant intra- and intermolecular relaxation contributions to the {sup 1}H spin-lattice relaxation as well as by benefiting from the universal low-frequency dispersion law characteristic of Fickian diffusion which yields, at low frequencies, a linear dependence of R{sub 1} on square root of frequency. From the {sup 19}F relaxation both anion and cation diffusion coefficients are determined for BMIM-PF{sub 6}. The diffusion coefficients obtained from FC NMR relaxometry are in good agreement with results reported from pulsed- field-gradient NMR. This shows that NMR relaxometry can be considered as an alternative route of determining diffusion coefficients of both cations and anions in ionic liquids.

  19. A visible-light-promoted aerobic metal-free C-3 thiocyanation of indoles.

    PubMed

    Fan, Weigang; Yang, Qi; Xu, Fengshan; Li, Pixu

    2014-11-01

    A simple and efficient visible-light-promoted method for the C-3 thiocyanation of indoles has been developed. The transformation uses Rose Bengal as the photocatalyst and air as the terminal oxidant. The reaction is mild, high-yielding, and environmentally benign.

  20. Creatinine adjustment of spot urine samples and 24 h excretion of iodine, selenium, perchlorate, and thiocyanate.

    PubMed

    Ohira, Shin-ichi; Kirk, Andrea B; Dyke, Jason V; Dasgupta, Purnendu K

    2008-12-15

    Creatinine (CR) adjustment is widely used for the estimation of urinary 24 h excretion from spot urine samples. We have compared CR-adjusted values for urinary iodine, selenium, perchlorate, and thiocyanate to measured 24 h excretion. The urine samples were collected from a cohort of 14 breastfeeding mothers with both spot samples and 24 h collection, 52 24 h and spot sample pairs where the 24 h CR value fell within the "normal" adult female CR excretion range of 0.6-1.6 g/day were considered for this analysis. In addition, a nonlactating female and a male subject provided all micturitions for 1 and 5 days, respectively. Creatinine was analyzed with a Jáffe reaction-based automated analyzer. Iodine and selenium were determined with induction coupled plasma-mass spectrometry (ICP-MS). Perchlorate and thiocyanate were measured with ion chromatography (IC)-isotope dilution tandem mass spectrometry (MS/MS). Creatinine-adjusted values were poor substitutes of the actual 24 h excretion values (average deviation +/-69, 78, 105, and 104% for iodine, selenium, perchlorate, and thiocyanate, respectively.). Over a 5 day period, the 24 h iodine excretion predicted based on creatinine adjustment of spot samples for the same individual deviated between -83.5 to +101% from the actual measured value, the minimum absolute error being 2.5%. Creatinine adjustment for estimation of 24 h excretion from spot samples was not effective for iodine, selenium, perchlorate, or thiocyanate.

  1. Role of thiocyanate ion in detoxification of the anticancer agent chlorambucil.

    PubMed

    Hovinen, J; Pettersson-Fernholm, T; Lahti, M; Vilpo, J

    1998-11-01

    N,N-Bis(2-chloroethyl)-p-aminophenylbutyric acid (chlorambucil, 1) is an orally administrated drug widely used in the chemotherapy of chronic lymphocytic leukemia. We have recently described a new metabolic path for the decomposition of 1 in human gastric juice based on its reactions with saliva-derived thiocyanate ion. We report here our quantitative data on the reactions of thiocyanate ion with CLB in various fluid matrixes at 37 degreesC. The rate of decomposition of 1 is zero-order with respect to SCN- concentration up to 100 mM. However, thiocyanate ion reacts ca. 18 300 times faster than water with the aziridinium ion derived from 1 at neutral and acidic pH. When the SCN- concentration was greater than 10 mM, practically no N,N-bis(2-hydroxyethyl)-p-aminophenylbutyric acid, 4, the product of chlorambucil hydrolysis, could be detected. Thiocyanate ion also effectively overcompensates for the rate retardation caused by Cl-; 10 mM SCN- is enough to decrease the effect of 0.5 M chloride ion to one-half. This is an important factor in human gastric juice where the chloride ion concentration is normally high.

  2. Comparative effects of prolonged administration of cyanide, thiocyanate and chokecherry (Prunus virginiana) to goats

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The aim of the present study was to determine and compare the clinical, hematological, biochemical, and histopathological changes induced by cyanide, thiocyanate, and chokecherry (Prunus virginiana) in goats. Sixteen Boer-Spanish cross-bred female goats were divided into 4 treatment groups: 1) contr...

  3. Perchlorate, thiocyanate, and nitrate in edible cole crops (Brassica sp.) produced in the lower Colorado River region.

    PubMed

    Sanchez, C A; Blount, B C; Valentin-Blasini, L; Krieger, R I

    2007-12-01

    The Colorado River is contaminated with low levels of perchlorate. Perchlorate has the potential to disrupt thyroid function by inhibiting the uptake of iodide. Brassica are rich sources of thiocyanate and nitrate, also inhibitors of iodide uptake. This study was conducted to estimate potential human exposure to perchlorate, thiocyanate, and nitrate from Brassica sp. irrigated with Colorado River water. Results indicate that Brassica sp. irrigated with Colorado River water do accumulate trace levels of perchlorate. However, the levels of perchlorate observed are low relative to the nitrate and thiocyanate naturally present in these species and low relative to the reference dose recommended by the NAS and the USEPA. PMID:17962898

  4. A practical synthesis of 3,4-diethoxybenzthioamide based on Friedel-Crafts reaction with potassium thiocyanate in methanesulfonic acid.

    PubMed

    Aki, Shinji; Fujioka, Takafumi; Ishigami, Masashi; Minamikawa, Jun-ichi

    2002-09-01

    The synthesis of 3,4-diethoxybenzthioamide, the key intermediate for OPC-6535, is achieved by employing Friedel-Crafts reaction of 1,2-diethoxybenzene with potassium thiocyanate in methanesulfonic acid at ambient temperature.

  5. Ion pairs of a molybdenum thiocyanate complex with dyes of the xanthene series

    SciTech Connect

    Ganago, L.I.; Ivanova, I.F.

    1988-03-10

    It has been ascertained that thiocyanate complexes of molybdenum react with dyes of the xanthene series, Rhodamine 6G and Rhodamine B, to form ion pairs. The Mo:SCN:Rhod. component ratios are respectively 1:5:2 and 1:6:3. The ion pairs are stable in an acid medium: 4.5-5.5 M H/sub 2/SO/sub 4/ (MTC-Rhod. 6G) and 3 M H/sub 2/SO (MTC-Rhod. B), and their molecular extinction coefficients are 2.22 x 10/sup 5/ and 3.8 x 10/sub 5/ respectively; MTC in a molybdenum thiocyanate complex. A procedure has been worked out for determining molybdenum in films, making use of the reaction of forming an MTC-Rhod. B ion pair.

  6. A solvent extraction study of molybdenum chloride and molybdenum thiocyanate complexes

    USGS Publications Warehouse

    Greenland, L.P.; Lillie, E.G.

    1974-01-01

    The effect of reducing agents on molybdenum(VI) solutions in hydrochloric acid was studied by a solvent extraction technique to elucidate the composition of the colored molybdenum thiocyanate complex. Neither copper(I) chloride nor ascorbic acid have any effect on the extraction of MoO2Cl2; it is inferred that tin(II) chloride reduces Mo(VI) stepwise to a polynuclear Mo(V)??Mo(VI) complex and then to Mo(V). The colored thiocyanate complex produced by copper(I) and by ascorbic acid differs only slightly in extraction characteristics from the uncolored Mo(VI) complex. It is suggested that the color may be produced by an isomerization reaction of MoO2(SCN)2, and thus that the colored species may be a hexavalent rather than pentavalent molybdenum complex. ?? 1974.

  7. Oxidation of ferrocene by thiocyanic acid in the presence of ammonium oxalate

    NASA Astrophysics Data System (ADS)

    Ruslin, Farah bt; Yamin, Bohari M.

    2014-09-01

    A flake-like crystalline salt was obtained from the reaction of ferrocene, oxalic acid and ammonium thiocyanate in ethanol The elemental analysis and spectroscopic data were in agreement with the preliminary X-ray molecular structure. The compound consists of four ferrocenium moieties and a counter anion consisting of two (tetraisothiocyanato)iron(III) linked by an oxalato bridging group in such a way that both iron central atoms adopt octahedral geometries.

  8. Oxidation of ferrocene by thiocyanic acid in the presence of ammonium oxalate

    SciTech Connect

    Ruslin, Farah bt; Yamin, Bohari M.

    2014-09-03

    A flake-like crystalline salt was obtained from the reaction of ferrocene, oxalic acid and ammonium thiocyanate in ethanol The elemental analysis and spectroscopic data were in agreement with the preliminary X-ray molecular structure. The compound consists of four ferrocenium moieties and a counter anion consisting of two (tetraisothiocyanato)iron(III) linked by an oxalato bridging group in such a way that both iron central atoms adopt octahedral geometries.

  9. Studies on extraction of beryllium from thiocyanate solutions by quaternary ammonium halides.

    PubMed

    El-Yamani, I S; El-Messieh, E N

    A 0.4M tricaprylmethylammonium chloride solution in n-hexane was used for the quantitative extraction of beryllium from hydrochloric acid (pH 3) and 5M potassium thiocyanate. Beryllium was stripped from the organic phase with 1M sodium hydroxide, then determined volumetrically with bismuthyl perchlorate and bromocresol green indicator. Beryllium was extracted in presence of a large number of elements which are usually associated with it in beryl and in fission products of nuclear fuel.

  10. Thiocyanate in food and iodine in milk: from domestic animal feeding to improved understanding of cretinism.

    PubMed

    Laurberg, Peter; Andersen, Stig; Knudsen, Nils; Ovesen, Lars; Nøhr, Susanne B; Bülow Pedersen, Inge

    2002-10-01

    Transport of iodine in the mammary gland into breast milk plays a central role in various fields of prevention of thyroid diseases. First, a sufficient content of iodine in the mother's milk is necessary for normal brain development in the breastfed child. This is attained by expression during lactation in the mammary gland of the sodium iodide symporter (NIS), also responsible for iodine transport in the thyroid. Milk iodine content varies with the iodine intake of the mother, and urinary iodine excretion in groups of mothers seems to be a valuable indicator of the iodine status of their breastfed children. Second, iodine in dairy products provides a considerable part of iodine intake in many populations. Thiocyanate from rapeseed feeding of cows decreases milk iodine content, probably by competitive inhibition of NIS in the mammary gland. Alterations in feeding of dairy cows may alter the iodine content of consumer milk, and this may influence the risk of thyroid diseases in the population. Thiocyanate inhibition of iodine transport into milk may also be operative in humans with a high thiocyanate intake. This could further impair iodine status in breastfed children in low-iodine intake areas of the world. It can be speculated that a low-iodine content of mother's milk because of inhibition of NIS in the mammary gland may be one factor of importance for development of myxedematous cretinism.

  11. Urinary thiocyanate concentrations are associated with adult cancer and lung problems: US NHANES, 2009-2012.

    PubMed

    Shiue, Ivy

    2015-04-01

    Links between environmental chemicals and human health have emerged but the effects from perchlorate, nitrate and thiocyanate were unclear. Therefore, it was aimed to study the relationships of urinary perchlorate, nitrate and thiocyanate concentrations and adult health conditions in a national and population-based study. Data was retrieved from US National Health and Nutrition Examination Surveys, 2009-2012, including demographics, blood pressure readings, self-reported health conditions and urinary perchlorate, nitrate and thiocyanate concentrations. Analyses included chi-square test, t test survey-weighted logistic regression models and population attributable risk estimation. There were no clear associations between urinary perchlorate concentrations and adult health conditions, although people with hearing loss and diabetes could be at the borderline risk. Urinary thiocyanate concentrations were significantly associated with emphysema (odds ratio (OR) 2.70 95% confidence intervals (CI) 1.91-3.82, P < 0.001), cancer (OR 1.21 95%CI 1.06-1.39, P = 0.008), chronic bronchitis (OR 1.23 95%CI 1.10-1.52, P = 0.003), wheezing (OR 1.24 95%CI 1.05-1.46, P = 0.011), coughing (OR 1.19 95%CI 1.03-1.37, P = 0.018) and sleep complaints (OR 1.14 95%CI 1.02-1.26, P = 0.019). The population attributable risks accounted for 3.3% (1.8-5.3%), 1.9% (0.6-3.5%), 1.2% (0.5-2.6%), 2.2% (0.5-4.1%), 1.8% (0.3-6.2%) and 1.3% (0.2-2.4%) for emphysema, cancer, chronic bronchitis, wheezing, coughing and sleep complaints, respectively. In addition, there was an inverse association observed between urinary nitrate level and heart failure. This is for the first time observing significant risk effects of urinary thiocyanate concentrations on adult cancer and lung problems, although the causality cannot be established. Elimination of such environmental chemical in humans should be included in future health policy and intervention programs. PMID:25367645

  12. Urinary thiocyanate concentrations are associated with adult cancer and lung problems: US NHANES, 2009-2012.

    PubMed

    Shiue, Ivy

    2015-04-01

    Links between environmental chemicals and human health have emerged but the effects from perchlorate, nitrate and thiocyanate were unclear. Therefore, it was aimed to study the relationships of urinary perchlorate, nitrate and thiocyanate concentrations and adult health conditions in a national and population-based study. Data was retrieved from US National Health and Nutrition Examination Surveys, 2009-2012, including demographics, blood pressure readings, self-reported health conditions and urinary perchlorate, nitrate and thiocyanate concentrations. Analyses included chi-square test, t test survey-weighted logistic regression models and population attributable risk estimation. There were no clear associations between urinary perchlorate concentrations and adult health conditions, although people with hearing loss and diabetes could be at the borderline risk. Urinary thiocyanate concentrations were significantly associated with emphysema (odds ratio (OR) 2.70 95% confidence intervals (CI) 1.91-3.82, P < 0.001), cancer (OR 1.21 95%CI 1.06-1.39, P = 0.008), chronic bronchitis (OR 1.23 95%CI 1.10-1.52, P = 0.003), wheezing (OR 1.24 95%CI 1.05-1.46, P = 0.011), coughing (OR 1.19 95%CI 1.03-1.37, P = 0.018) and sleep complaints (OR 1.14 95%CI 1.02-1.26, P = 0.019). The population attributable risks accounted for 3.3% (1.8-5.3%), 1.9% (0.6-3.5%), 1.2% (0.5-2.6%), 2.2% (0.5-4.1%), 1.8% (0.3-6.2%) and 1.3% (0.2-2.4%) for emphysema, cancer, chronic bronchitis, wheezing, coughing and sleep complaints, respectively. In addition, there was an inverse association observed between urinary nitrate level and heart failure. This is for the first time observing significant risk effects of urinary thiocyanate concentrations on adult cancer and lung problems, although the causality cannot be established. Elimination of such environmental chemical in humans should be included in future health policy and intervention programs.

  13. Concentrations of thiocyanate and goitrin in human plasma, their precursor concentrations in brassica vegetables, and associated potential risk for hypothyroidism.

    PubMed

    Felker, Peter; Bunch, Ronald; Leung, Angela M

    2016-04-01

    Brassica vegetables are common components of the diet and have beneficial as well as potentially adverse health effects. Following enzymatic breakdown, some glucosinolates in brassica vegetables produce sulforaphane, phenethyl, and indolylic isothiocyanates that possess anticarcinogenic activity. In contrast, progoitrin and indolylic glucosinolates degrade to goitrin and thiocyanate, respectively, and may decrease thyroid hormone production. Radioiodine uptake to the thyroid is inhibited by 194 μmol of goitrin, but not by 77 μmol of goitrin. Collards, Brussels sprouts, and some Russian kale (Brassica napus) contain sufficient goitrin to potentially decrease iodine uptake by the thyroid. However, turnip tops, commercial broccoli, broccoli rabe, and kale belonging to Brassica oleracae contain less than 10 μmol of goitrin per 100-g serving and can be considered of minimal risk. Using sulforaphane plasma levels following glucoraphanin ingestion as a surrogate for thiocyanate plasma concentrations after indole glucosinolate ingestion, the maximum thiocyanate contribution from indole glucosinolate degradation is estimated to be 10 μM, which is significantly lower than background plasma thiocyanate concentrations (40-69 μM). Thiocyanate generated from consumption of indole glucosinolate can be assumed to have minimal adverse risks for thyroid health.

  14. Biodegradation Of Thiocyanate Using Microbial Consortia Cultured From Gold Mine Tailings

    NASA Astrophysics Data System (ADS)

    Moreau, J. W.; Watts, M. P.; Spurr, L. P.; Vu, H. P.

    2015-12-01

    Some bacteria possess the capability to degrade SCN-; therefore, harnessing this metabolic trait offers a biotechnological remediation strategy for SCN- produced in gold ore processing. A tailings storage facility (TSF) at a gold mine in Victoria, Australia holds large quantities of thiocyanate (SCN-) contaminated mine waste. The surface water in the TSF typically contains SCN- concentrations of >800 mg L-1, and seepage from the facility has contaminated the groundwater at the site. This study aimed to culture SCN-degrading microbes from the TSF, characterize the microbial consortia and test its operational parameters for use in a thiocyanate-degrading bioreactor. Surface samples were obtained from several locations around the TSF facility and used to inoculate medium reflective of the moderately saline and alkaline tailings water at the TSF, in the absence of organic carbon but subject to additions of phosphate and trace metals. Four microbial consortia capable of rapid SCN- degradation were successfully cultured. Sequencing of 16S rRNA genes found that the consortia were dominated by Thiobacillus species, a genus of known SCN- degraders. Lower abundances of other SCN- degraders; Sphingopyxis and Rhodobacter, were also identified. The impact of a number of geochemical conditions, including pH, temperature and SCN- concentration, upon the growth and SCN- degrading capacity of these consortia was determined. These results informed the optimization of a lab-scale thiocyanate degrading bioreactor. In summary, the cultured bacterial consortia proved effective towards SCN- degradation at the prevailing geochemical conditions of the TSF, requiring minimal nutrient additions. These consortia were dominated by genera of known autotrophic SCN- degraders. The comprehensive characterisation of these SCN- degrading consortia will provide the fundamental operational parameters required for deployment of this technique at the field scale.

  15. Perinatal exposure to perchlorate, thiocyanate, and nitrate in New Jersey mothers and newborns

    PubMed Central

    Blount, Benjamin C.; Rich, David Q.; Valentin-Blasini, Liza; Lashley, Susan; Ananth, Cande V.; Murphy, Eileen; Smulian, John C.; Spain, Betty J.; Barr, Dana B.; Ledoux, Thomas; Hore, Paromita; Robson, Mark

    2009-01-01

    Perchlorate is a commonly occurring environmental toxicant that may be transported across the placental barrier by the sodium-iodide symporter (NIS), possibly resulting in both increased perchlorate exposure and decreased iodide uptake by the fetus. Therefore, we measured levels of three physiologically relevant NIS-inhibitors (perchlorate, nitrate and thiocyanate) and iodide in maternal and fetal fluids collected during cesarean-section surgeries on 150 U.S. women. Geometric means of perchlorate, thiocyanate and nitrate levels in maternal urine (2.90, 947 and 47900 µg/L, respectively) were similar to previously published results, while urinary iodide levels (1420 µg/L) were significantly higher (p<0.0001), likely because of prevalent prenatal vitamin use in the study population (74%). Thiocyanate levels were higher in the maternal serum, cord serum, and amniotic fluid of smokers compared to women with environmental tobacco smoke exposure and non-smokers (p-values of 0.0006, p=0.0011, and 0.0026, respectively). Perchlorate was detected in most samples: urine (100%), maternal serum (94%), cord serum (67%), and amniotic fluid (97%). Maternal urinary perchlorate levels were positively correlated with perchlorate levels in amniotic fluid (r=0.57), indicating that maternal urine perchlorate is an effective biomarker of fetal perchlorate exposure. Maternal serum perchlorate was generally higher than cord serum perchlorate (median ratio 2.4:1 for paired samples), and maternal urine perchlorate was always higher than fetal amniotic fluid perchlorate levels (mean ratio 22:1); conversely, iodide levels were typically higher in fetal fluids compared to maternal fluids. We found no evidence of either disproportionate perchlorate accumulation or lack of iodide in the fetal compartment. In this panel of healthy infants, we found no association between cord blood levels of these anions and newborn weight, length and head circumference. PMID:19848174

  16. Adsorption properties of decyl thiocyanate and decanethiol on platinum substrates studied by sum-frequency generation spectroscopy

    NASA Astrophysics Data System (ADS)

    Sartenaer, Yannick; Dreesen, Laurent; Humbert, Christophe; Volcke, Cédric; Tourillon, Gérard; Louette, Pierre; Thiry, Paul A.; Peremans, André

    2007-03-01

    Recently, thiocyanate groups were successfully used as precursors for thiolate assemblies. Indeed, they provide a useful alternative to thiol groups for self-assembly on metallic substrates. In order to check the adsorption properties and the quality of the thiocyanate-based self-assembled monolayers (SAMs), we use sum-frequency generation spectroscopy (SFG) and apply it to characterize the ad-layers of two similar molecules: decanethiol (DT) and decyl thiocyanate (DTCN) adsorbed on platinum surfaces. By comparing the SFG signals of the methyl and methylene vibration modes, we show that DTCN SAMs are less ordered than DT ones. These effects are related to the SAMs quality which depends on the molecular packing as highlighted by scanning tunnelling microscopy and X-ray photoelectron spectroscopy.

  17. Temperature dependence of chloride, bromide, iodide, thiocyanate and salicylate transport in human red cells

    PubMed Central

    Dalmark, Mads; Wieth, Jens Otto

    1972-01-01

    1. The temperature dependence of the steady-state self-exchange of chloride between human red cells and a plasma-like electrolyte medium has been studied by measuring the rate of 36Cl- efflux from radioactively labelled cells. Between 0 and 10° C the rate increased by a factor of eight corresponding to an Arrhenius activation energy of 33 kcal/mole. 2. The rate of chloride exchange decreased significantly in experiments where 95% of the chloride ions in cells and medium were replaced by other monovalent anions of a lyotropic series. The rate of chloride self-exchange was increasingly reduced by bromide, bicarbonate, nitrate, iodide, thiocyanate, and salicylate. The latter aromatic anion was by far the most potent inhibitor, reducing the rate of chloride self-exchange to 0·2% of the value found in a chloride medium. 3. The temperature sensitivity of the chloride self-exchange was not affected significantly by the anionic inhibitors. The Arrhenius activation energies of chloride exchange were between 30 and 40 kcal/mole in the presence of the six inhibitory anions mentioned above. 4. The rate of self-exchange of bromide, thiocyanate, and iodide between human red cells and media was determined after washing and labelling cells in media containing 120 mM bromide, thiocyanate, or iodide respectively. The rate of self-exchange of the three anions were 12, 3, and 0·4% of the rate of chloride self-exchange found in the chloride medium. 5. The Arrhenius activation energies of the self-exchange of bromide, iodide, and thiocyanate were all between 29 and 37 kcal/mole, the same magnitude as found for the self-exchange of chloride. 6. Although approximately 40% of the intracellular iodide and salicylate ions appeared to be adsorbed to intracellular proteins, the rate of tracer anion efflux followed first order kinetics until at least 98% of the intracellular anions had been exchanged. 7. The self-exchange of salicylate across the human red cell membrane occurred by a

  18. [Excess of thiocyanate and selenium deficiency: cofactors in the etiology of endemic goiter and cretinism in North Zaire].

    PubMed

    Thilly, C H; Contempre, B; Vanderpas, J B

    1990-01-01

    Endemic goitre is accompanied by a spectrum of iodine deficiency disorders (IDD). From work undertaken by CEMUBAC in Ubangui Zaïre, the role of thiocyanate overload is recalled while this work demonstrates for the first time in man an action of selenium supplementation (and thus deficiency) on thyroid function in iodine deficient areas. The extreme severity of the selenium deficiency may intervene either on the central and/or peripheral deiodination of thyroxine, or on the synthesis of the thyroid hormones. Together with thiocyanate overload, selenium deficiency may be responsible of the high frequency of myxedematous cretins in Zaïre. PMID:2099229

  19. Determination of thiocyanate in saliva by headspace gas chromatography-mass spectrometry, following a single-step aqueous derivatization with triethyloxonium tetrafluoroborate.

    PubMed

    Ammazzini, Sara; Onor, Massimo; Pagliano, Enea; Mester, Zoltán; Campanella, Beatrice; Pitzalis, Emanuela; Bramanti, Emilia; D'Ulivo, Alessandro

    2015-06-26

    A novel method for the determination of salivary thiocyanate is presented. Thiocyanate was converted into ethyl thiocyanate by single-step aqueous derivatization based on triethyloxonium tetrafluoroborate and measured by gas chromatography-mass spectrometry (15 min runtime). The ethyl thiocyanate derivative is volatile and can be sampled from the headspace. The derivatization chemistry proposed allows for separation of the analyte from saliva matrix whose introduction in the measurement system is avoided. Quantitation of the analyte was obtained by isotope dilution, employing a (13)C-enriched thiocyanate as internal standard. Technical details and fundamental aspects of derivatization chemistry and calibration strategy are presented. The method was validated by comparison with a standard method based on ion chromatography. The two independent methodologies produced results in agreement within 3%. Also a three level spike recovery test was carried out for validation purpose and quantitative recoveries were attained. The method is fast, simple, safe, and sensitive. Measurement of a 1 mL volume 50 ng/g of thiocyanate standard produced a signal-to-noise ratio of 250 for the analytical peak. This method is therefore suitable for ultra-trace determination of thiocyanate (low part-per-billion range). For the application described the full detection potential of the method was not required and the sample preparation presented has been designed for quantitation of saliva samples containing 1-400 μg/g of thiocyanate with a combined standard uncertainty of 2% relative for saliva samples containing 25 μg/g of thiocyanate. This method was applied for the determination of thiocyanate in human saliva samples.

  20. Temporal variability in urinary concentrations of perchlorate, nitrate, thiocyanate and iodide among children

    PubMed Central

    MERVISH, NANCY; BLOUNT, BEN; VALENTIN-BLASINI, LIZA; BRENNER, BARBARA; GALVEZ, MAIDA P.; WOLFF, MARY S.; TEITELBAUM, SUSAN L.

    2012-01-01

    Perchlorate, nitrate and thiocyanate are ubiquitous in the environment, and human exposure to these chemicals is accurately measured in urine. Biomarkers of these chemicals represent a person's recent exposure, however, little is known on the temporal variability of the use of a single measurement of these biomarkers. Healthy Hispanic and Black children (6–10-year-old) donated urine samples over 6 months. To assess temporal variability, we used three statistical methods (n = 29; 153 urine samples): intraclass correlation coefficient (ICC), Spearman's correlation coefficient between concentrations measured at different timepoints and surrogate category analysis to assess how well tertile ranking by a single biomarker measurement represented the average concentration over 6 months. The ICC measure of reproducibility was poor (0.10–0.12) for perchlorate, nitrate and iodide; and fair for thiocyanate (0.36). The correlations for each biomarker across multiple sampling times ranged from 0.01–0.57. Surrogate analysis showed consistent results for almost every surrogate tertile. Results demonstrate fair temporal reliability in the spot urine concentrations of the three NIS inhibitors and iodide. Surrogate analysis show that single-spot urine samples reliably categorize participant's exposure providing support for the use of a single sample as an exposure measure in epidemiological studies that use relative ranking of exposure. PMID:22166811

  1. Temporal variability in urinary concentrations of perchlorate, nitrate, thiocyanate and iodide among children.

    PubMed

    Mervish, Nancy; Blount, Ben; Valentin-Blasini, Liza; Brenner, Barbara; Galvez, Maida P; Wolff, Mary S; Teitelbaum, Susan L

    2012-01-01

    Perchlorate, nitrate and thiocyanate are ubiquitous in the environment, and human exposure to these chemicals is accurately measured in urine. Biomarkers of these chemicals represent a person's recent exposure, however, little is known on the temporal variability of the use of a single measurement of these biomarkers. Healthy Hispanic and Black children (6-10-year-old) donated urine samples over 6 months. To assess temporal variability, we used three statistical methods (n=29; 153 urine samples): intraclass correlation coefficient (ICC), Spearman's correlation coefficient between concentrations measured at different timepoints and surrogate category analysis to assess how well tertile ranking by a single biomarker measurement represented the average concentration over 6 months. The ICC measure of reproducibility was poor (0.10-0.12) for perchlorate, nitrate and iodide; and fair for thiocyanate (0.36). The correlations for each biomarker across multiple sampling times ranged from 0.01-0.57. Surrogate analysis showed consistent results for almost every surrogate tertile. Results demonstrate fair temporal reliability in the spot urine concentrations of the three NIS inhibitors and iodide. Surrogate analysis show that single-spot urine samples reliably categorize participant's exposure providing support for the use of a single sample as an exposure measure in epidemiological studies that use relative ranking of exposure.

  2. Comparative study of decyl thiocyanate and decanethiol self-assembled monolayers on gold substrates

    NASA Astrophysics Data System (ADS)

    Dreesen, L.; Volcke, C.; Sartenaer, Y.; Peremans, A.; Thiry, P. A.; Humbert, C.; Grugier, J.; Marchand-Brynaert, J.

    2006-09-01

    In a recent paper Ciszek et al. [J.W. Ciszek, M.P. Stewart, J.M. Tour, J. Am. Chem. Soc. 126 (2004) 13172] showed that organic thiocyanates may be an interesting alternative to the use of thiols for thiolate assemblies. We use scanning tunnelling microscopy (STM), infrared reflection absorption and sum-frequency generation spectroscopies (IRRAS and SFG) in order to study the adsorption properties of decyl thiocyanates (DTCN) and compare them to the decanethiol (DT) ones. Firstly, IRRAS measurements show that DTCN molecules form self-assembled monolayers (SAMs) on gold via a thiolate link with the metallic substrate. Secondly, the DTCN SAM on gold is less ordered than the DT one as highlighted by SFG spectroscopy. Indeed, the intensities of the methyl vibration modes vanish while the methylene ones increase when DTCN molecules are adsorbed on the substrate instead of DT. We explain the differences in SAMs quality on the basis of STM measurements which reveal differences in molecular order and packing.

  3. Surface-enhanced raman scattering from silver-cyanide and silver-thiocyanate vibrations and the importance of adatoms

    NASA Astrophysics Data System (ADS)

    Wetzel, H.; Gerischer, H.; Pettinger, B.

    1981-05-01

    Surface-enhanced Raman scattering (SERS) has been studied for silver-cyanide and 3-thiocyanate vibrations at 221 and 2111 cm -1 and at 218 and 2132 cm -1, respectively. We report evidence that besides large-scale surface roughness the presence of adatoms is mandatory in order to obtain SERS.

  4. Employing Lead Thiocyanate Additive to Reduce the Hysteresis and Boost the Fill Factor of Planar Perovskite Solar Cells.

    PubMed

    Ke, Weijun; Xiao, Chuanxiao; Wang, Changlei; Saparov, Bayrammurad; Duan, Hsin-Sheng; Zhao, Dewei; Xiao, Zewen; Schulz, Philip; Harvey, Steven P; Liao, Weiqiang; Meng, Weiwei; Yu, Yue; Cimaroli, Alexander J; Jiang, Chun-Sheng; Zhu, Kai; Al-Jassim, Mowafak; Fang, Guojia; Mitzi, David B; Yan, Yanfa

    2016-07-01

    Lead thiocyanate in the perovskite precursor can increase the grain size of a perovskite thin film and reduce the conductivity of the grain boundaries, leading to perovskite solar cells with reduced hysteresis and enhanced fill factor. A planar perovskite solar cell with grain boundary and interface passivation achieves a steady-state efficiency of 18.42%.

  5. Simple and Inexpensive Computer Interface to a Durrum Stopped-Flow Apparatus Tested Using the Iron (III)--Thiocyanate Reaction

    ERIC Educational Resources Information Center

    Hoag, Craig M.

    2005-01-01

    A simple Vernier software and Technology LabPro unit was used to interface a computer with a Durrum model 110 stopped-flow apparatus using the iron (III)--thiocyanate reaction. The software can readily be used to retrieve that data from the stopped-flow apparatus using one probe to measure the voltage and a second probe to trigger the data…

  6. Synthesis and characterization of bis nitrato[4-hydroxyacetophenonesemicarbazone) nickel(II) complex as ionophore for thiocyanate-selective electrode.

    PubMed

    Chandra, Sulekh; Hooda, Sunita; Tomar, Praveen Kumar; Malik, Amrita; Kumar, Ankit; Malik, Sakshi; Gautam, Seema

    2016-05-01

    The PVC based-ion selective electrode viz., bis nitrato[4-hydroxyacetophenone semicarbazone] nickel(II) as an ionophore was prepared for the determination of thiocyanate ion. The ionophore was characterized by FT-IR, UV-vis, XRD, magnetic moment and elemental analysis (CHN). On the basis of spectral studies an octahedral geometry has been assigned. The best performance was obtained with a membrane composition of 31% PVC, 63% 2-nitrophenyl octylether, 4.0% ionophore and 2.0% trioctylmethyl ammonium chloride. The electrode exhibited an excellent Nernstian response to SCN(-) ion ranging from 1.0 × 10(-7) to 1.0 × 10(-1)M with a detection limit of 8.6 × 10(-8)M and a slope of -59.4 ± 0.2 mV/decade over a wide pH range (1.8-10.7) with a fast response time (6s) at 25 °C. The proposed electrode showed high selectivity for thiocyanate ion over a number of common inorganic and organic anions. It was successfully applied to direct determination of thiocyanate in biological (urine and saliva) samples in order to distinguish between smokers and non-smokers, environmental samples and as an indicator electrode for titration of thiocyanate ions with AgNO3 solution. PMID:26952393

  7. Copper thiocyanate: An attractive hole transport/extraction layer for use in organic photovoltaic cells

    SciTech Connect

    Treat, Neil D. E-mail: t.anthopoulos@imperial.ac.uk; Stingelin, Natalie; Yaacobi-Gross, Nir; Faber, Hendrik; Perumal, Ajay K.; Bradley, Donal D. C.; Anthopoulos, Thomas D. E-mail: t.anthopoulos@imperial.ac.uk

    2015-07-06

    We report the advantageous properties of the inorganic molecular semiconductor copper(I) thiocyanate (CuSCN) for use as a hole collection/transport layer (HTL) in organic photovoltaic (OPV) cells. CuSCN possesses desirable HTL energy levels [i.e., valence band at −5.35 eV, 0.35 eV deeper than poly(3,4-ethylenedioxythiophene):polystyrenesulfonate (PEDOT:PSS)], which produces a 17% increase in power conversion efficiency (PCE) relative to PEDOT:PSS-based devices. In addition, a two-fold increase in shunt resistance for the solar cells measured in dark conditions is achieved. Ultimately, CuSCN enables polymer:fullerene based OPV cells to achieve PCE > 8%. CuSCN continues to offer promise as a chemically stable and straightforward replacement for the commonly used PEDOT:PSS.

  8. Extractive spectrophotometric determination of niobium(V) with thiocyanate and amides

    SciTech Connect

    Patel, K.S. ); Das, M. )

    1991-07-01

    A new procedure for extractive spectrophotometric determination of niobium(V) with thiocyanate and 10 amides (derived from condensation of aceticanhydride with amines) is described. The value of molar absorptivity of the complexes in benzene lie in the range of (3.10 - 4.20){times}10{sup 4} 1 mole{sup {minus}1} cm{sup {minus}1} at absorption maximum 395 - 400 nm. Among these, the most sensitive compound, N-octylacetamide has been chosen for the detailed studies. The limit for detection is 0.01 {mu}g Nb/ml of the aqueous solution. The effect of various analytical variables on the determination of the metal has been examined. The method is simple, rapid and being free from interferences of almost all metal ions except Mo. Its application for the analysis of the metal to ore, slag, steel and water has been tested.

  9. A New Composition for Co(II)-porphyrin-based Membranes Used in Thiocyanate-selective Electrodes

    PubMed Central

    Vlascici, Dana; Fagadar-Cosma, Eugenia; Bizerea-Spiridon, Otilia

    2006-01-01

    In the present paper, the potentiometric response characteristics of a metalloporphyrin-based electrode in o-nitrophenyloctylether (o-NPOE) plasticized polyvinyl chloride (PVC) membrane are presented for a set of monovalent anions. As membrane ionophore, 5,10,15,20-tetrakis-(4-methoxyphenyl)-porphyrin-Co(II) (CoTMeOPP) was used. To establish the optimum composition of the membrane, different molar percents of cationic derivative (mol.% relative to ionophore) were used. Electrodes formulated with membranes containing 1 wt.% ionophore, 66 wt.% o-NPOE, 33 wt.% PVC (plasticizer: PVC = 2:1) and the lipophilic cationic derivative (35 mol%) are shown to exhibit high selectivity for thiocyanate with a near-Nernstian slope in the working concentration range of 1.0×10−1–1.0×10−5 M, with a good stability in time.

  10. Inactivation of yeast and filamentous fungi by the lactoperoxidase-hydrogen peroxide-thiocyanate-system.

    PubMed

    Popper, L; Knorr, D

    1997-02-01

    The antifungal activity of the lactoperoxidase (LPO) system with glucose oxidase (GOD) as source of hydrogen peroxide was determined in salt solution and in apple juice. The test organisms Rhodutorula rubra and Saccharomyces cerevisiae were cultivated aerobically in apple juice, Mucor rouxii was grown on wort agar adjusted to pH 4.5. Aspergillus niger and Byssochlamys fulva were kept on malt extract agar. Spores of the filamentous fungi were harvested by suspension in salt solution supplemented with Tween 80 and checked microscopically. The antifungal activity of the combined enzyme system was tested with initial counts of approx. 10(5) cfu.ml-1 (yeast cells or spores) suspended in salt solution supplemented with 25 mg.l-1 thiocyanate and 20 g.l-1 glucose or in apple juice supplemented with the same amount of thiocyanate. The tests were performed with 25 ml of the medium in 100 ml Erlenmeyer flasks shaken at 28 degrees C under aerobic conditions. Inactivation was achieved for all test organisms in both media. The yeast strains were found to be least stable while B. fulva was most resistant. A combination of 5 U.ml-1 LPO with 0.5 to 1 U.ml-1 GOD was sufficient for complete inactivation of this mold in salt solution within 2 h. The enzyme system also showed antifungal activity in apple juice at acid pH (3.2), although its effectiveness was reduced. In this medium, B. fulva was inactivated by 20 U.ml-1 LPD and 1 U.ml-1 GOD within 4 h. R. rubra and S. cerevisfiae were unable to survive in apple juice at 5 U.ml-1 LPO combined with 1 U.ml-1 GOD. For inhibition by GOD alone, higher amounts of this enzyme were needed and even then only M. rouxii and R. rubra have been affected within the concentration range tested (maximum 3 U.ml-1).

  11. Thiocyanate binding to the molybdenum centre of the periplasmic nitrate reductase from Paracoccus pantotrophus.

    PubMed

    Butler, C S; Charnock, J M; Garner, C D; Thomson, A J; Ferguson, S J; Berks, B C; Richardson, D J

    2000-12-15

    The periplasmic nitrate reductase (NAP) from Paracoccus pantotrophus is a soluble two-subunit enzyme (NapAB) that binds two haem groups, a [4Fe-4S] cluster and a bis(molybdopterin guanine dinucleotide) (MGD) cofactor that catalyses the reduction of nitrate to nitrite. In the present study the effect of KSCN (potassium thiocyanate) as an inhibitor and Mo ligand has been investigated. Results are presented that show NAP is sensitive to SCN(-) (thiocyanate) inhibition, with SCN(-) acting as a competitive inhibitor of nitrate (K(i) approximately 4.0 mM). The formation of a novel EPR Mo(V) species with an elevated g(av) value (g(av) approximately 1.994) compared to the Mo(V) High-g (resting) species was observed upon redox cycling in the presence of SCN(-). Mo K-edge EXAFS analysis of the dithionite-reduced NAP was best fitted as a mono-oxo Mo(IV) species with three Mo-S ligands at 2.35 A (1 A=0.1 nm) and a Mo-O ligand at 2.14 A. The addition of SCN(-) to the reduced Mo(IV) NAP generated a sample that was best fitted as a mono-oxo (1.70 A) Mo(IV) species with four Mo-S ligands at 2.34 A. Taken together, the competitive nature of SCN(-) inhibition of periplasmic nitrate reductase activity, the elevated Mo(V) EPR g(av) value following redox cycling in the presence of SCN(-) and the increase in sulphur co-ordination of Mo(IV) upon SCN(-) binding, provide strong evidence for the direct binding of SCN(-) via a sulphur atom to Mo. PMID:11104696

  12. Vibrational dynamics of thiocyanate and selenocyanate bound to horse heart myoglobin

    NASA Astrophysics Data System (ADS)

    Maj, Michał; Oh, Younjun; Park, Kwanghee; Lee, Jooyong; Kwak, Kyung-Won; Cho, Minhaeng

    2014-06-01

    The structure and vibrational dynamics of SCN- and SeCN-bound myoglobin have been investigated using polarization-controlled IR pump-probe measurements and quantum chemistry calculations. The complexes are found to be in low and high spin states, with the dominant contribution from the latter. In addition, the Mb:SCN high spin complex exhibits a doublet feature in the thiocyanate stretch IR absorption spectra, indicating two distinct molecular conformations around the heme pocket. The binding mode of the high spin complexes was assigned to occur through the nitrogen atom, contrary to the binding through the sulfur atom that was observed in myoglobin derived from Aplysia Limacina. The vibrational energy relaxation process has been found to occur substantially faster than those of free SCN- and SeCN- ions and neutral SCN- and SeCN-derivatized molecules reported previously. This supports the N-bound configurations of MbNCS and MbNCSe, because S- and Se-bound configurations are expected to have significantly long lifetimes due to the insulation effect by heavy bridge atom like S and Se in such IR probes. Nonetheless, even though their lifetimes are much shorter than those of corresponding free ions in water, the vibrational lifetimes determined for MbNCS and MbNCSe are still fairly long compared to those of azide and cyanide myoglobin systems studied before. Thus, thiocyanate and selenocyanate can be good local probes of local electrostatic environment in the heme pocket. The globin dependence on binding mode and vibrational dynamics is also discussed.

  13. Simultaneous spectrophotometric determination of cyanide and thiocyanate after separation on a melamine-formaldehyde resin.

    PubMed

    Gümüş, G; Demirata, B; Apak, R

    2000-11-01

    A simple indirect spectrophotometric method for the determination of cyanide, based on the oxidation of the cyanide with chlorine (Cl(2)) is described. The residual chlorine is determined by the color reaction with o-tolidine (3,3'-dimethylbenzidine). The maximum absorbance for Cl(2) is at 437 nm. A linear calibration graph (0-4.0x10(-5) M CN(-)) is obtained under optimal reaction conditions at room temperature and pH 11-12. The stoichiometric mole ratio of chlorine to cyanide is 1:1. The effective molar absorptivity for cyanide is 5.87x10(4) l mol(-1) cm(-1) at pH 1.6. The limit of quantification (LOQ) is 3.6x10(-7) M or 9.4 ppb. Effects of pH, excess reagent, sensitivity, reaction time and tolerance limits of interferent ions are reported. The method was applied to the determination of cyanide in a real sample. The basic interferent usually accompanying CN(-), i.e. thiocyanate, is separated from cyanide by sorption on a melamine-formaldehyde resin at pH 9 while cyanide is not retained. Thiocyanate is eluted with 0.4 M NaOH from the column and determined spectrophotometrically using the acidic FeCl(3) reagent. The initial column effluent containing cyanide was analyzed by both the developed chlorine-o-tolidine method and the conventional barbituric acid-pyridine (Spectroquant 14800) procedure, and the results were statistically compared. The developed method is relatively inexpensive and less laborious than the standard (Spectroquant) procedure, and insensitive to the common interferent, cyanate (CNO(-)).

  14. Purification of bovine milk lactoperoxidase and investigation of antibacterial properties at different thiocyanate mediated.

    PubMed

    Uğuz, M T; Ozdemir, H

    2005-01-01

    Bovine lactoperoxidase (LPO) was purified with amberlite CG 50 H+ resin, CM sephadex C-50 ion-exchange chromatography, and sephadex G-100 gel filtration chromatography from skim milk. The activity of lactoperoxidase was measured by using 2.2-azino-bis (3-ethylbenzthiazoline-6 sulfonic acid) diammonium salt (ABTS) as a choromogenic substrate at pH 6.0. Purification degree for the purified enzyme was controlled with SDS-PAGE and Rz value (A412/A280). Rz value for the purified LPO was 0.8. Km value at pH 6.0 at 20 degrees C for the LPO was 0.20 mM. Vmax value was 7.87 micromol/ml min at pH 6.0 at 20 degrees C. Bovine LPO showed high antibacterial activity in 100 mM thiocyanate--100 mM H2O2 medium for some pathogenic bacteria, such as Aeromonas hydrophila ATCC 7966, Micrococcus luteus LA 2971, Mycobacterium smegmatis RUT, Bacillus subtilis IMG 22, Pseudomonas pyocyanea, Bacillus subtilis var. niger ATCC 10, Pseudomonas aeruginosa ATCC 27853, Enterococcus faecalis ATCC 15753, Bacillus brevis FMC3, Klebsiella pneumoniae FMC 5, Corynebacterium xerosis UC 9165, Bacillus cereus EU, Bacillus megaterium NRS, Yersinia enterocolytica, Listeria monocytogenes scoot A, Bacillus megaterium EU, Bacillus megaterium DSM32, Klebsiella oxytocica, Staphylococcus aerogenes, Streptococcus faecalis, Mycobacterium smegmatis CCM 2067 and compared with well known antibacterial substances such as penicilline, ampicilline, amoxicillin-clavulanate and ceftriaxon. The LPO--100 mM thiocyanate--100 mM H2O2 system was purposed as an effective agent against many of the diseases causing organisms in human and animals.

  15. [Mechanism of cyanide and thiocyanate decomposition by an association of Pseudomonas putida and Pseudomonas stutzeri strains].

    PubMed

    Grigor'eva, N V; Kondrat'eva, T F; Krasil'nikova, E N; Karavaĭko, G I

    2006-01-01

    The intermediate and terminal products of cyanide and thiocyanate decomposition by individual strains of the genus Pseudomonas, P. putida strain 21 and P. stutzeri strain 18, and by their association were analyzed. The activity of the enzymes of nitrogen and sulfur metabolism in these strains was compared with that of the collection strains P. putida VKM B-2187T and P. stutzeri VKM B-975T. Upon the introduction of CN- and SCN- into cell suspensions of strains 18 and 21 in phosphate buffer (pH 8.8), the production of NH4+ was observed. Due to the high rate of their utilization, NH3, NH4+, and CNO- were absent from the culture liquids of P. putida strain 21 and P. stutzeri strain 18 grown with CN- or SCN-. Both Pseudomonas strains decomposed SCN- via cyanate production. The cyanase activity was 0.75 micromol/(min mg protein) for P. putida strain 21 and 1.26 micromol/(min mg protein) for P. stutzeri strain 18. The cyanase activity was present in the cells grown with SCN- but absent in cells grown with NH4+. Strain 21 of P. putida was a more active CN- decomposer than strain 18 of P. stutzeri. Ammonium and CO2 were the terminal nitrogen and carbon products of CN- and SCN- decomposition. The terminal sulfur products of SCN- decomposition by P. stutzeri strain 18 and P. putida strain 21 were thiosulfate and tetrathionate, respectively. The strains utilized the toxic compounds in the anabolism only, as sources of nitrogen (CN- and SCN-) and sulfur (SCN-). The pathway of thiocyanate decomposition by the association of bacteria of the genus Pseudomonas is proposed based on the results obtained.

  16. Vibrational dynamics of thiocyanate and selenocyanate bound to horse heart myoglobin

    SciTech Connect

    Maj, Michał; Oh, Younjun; Park, Kwanghee; Lee, Jooyong; Cho, Minhaeng; Kwak, Kyung-Won

    2014-06-21

    The structure and vibrational dynamics of SCN- and SeCN-bound myoglobin have been investigated using polarization-controlled IR pump-probe measurements and quantum chemistry calculations. The complexes are found to be in low and high spin states, with the dominant contribution from the latter. In addition, the Mb:SCN high spin complex exhibits a doublet feature in the thiocyanate stretch IR absorption spectra, indicating two distinct molecular conformations around the heme pocket. The binding mode of the high spin complexes was assigned to occur through the nitrogen atom, contrary to the binding through the sulfur atom that was observed in myoglobin derived from Aplysia Limacina. The vibrational energy relaxation process has been found to occur substantially faster than those of free SCN{sup −} and SeCN{sup −} ions and neutral SCN- and SeCN-derivatized molecules reported previously. This supports the N-bound configurations of MbNCS and MbNCSe, because S- and Se-bound configurations are expected to have significantly long lifetimes due to the insulation effect by heavy bridge atom like S and Se in such IR probes. Nonetheless, even though their lifetimes are much shorter than those of corresponding free ions in water, the vibrational lifetimes determined for MbNCS and MbNCSe are still fairly long compared to those of azide and cyanide myoglobin systems studied before. Thus, thiocyanate and selenocyanate can be good local probes of local electrostatic environment in the heme pocket. The globin dependence on binding mode and vibrational dynamics is also discussed.

  17. Vibrational dynamics of thiocyanate and selenocyanate bound to horse heart myoglobin.

    PubMed

    Maj, Michał; Oh, Younjun; Park, Kwanghee; Lee, Jooyong; Kwak, Kyung-Won; Cho, Minhaeng

    2014-06-21

    The structure and vibrational dynamics of SCN- and SeCN-bound myoglobin have been investigated using polarization-controlled IR pump-probe measurements and quantum chemistry calculations. The complexes are found to be in low and high spin states, with the dominant contribution from the latter. In addition, the Mb:SCN high spin complex exhibits a doublet feature in the thiocyanate stretch IR absorption spectra, indicating two distinct molecular conformations around the heme pocket. The binding mode of the high spin complexes was assigned to occur through the nitrogen atom, contrary to the binding through the sulfur atom that was observed in myoglobin derived from Aplysia Limacina. The vibrational energy relaxation process has been found to occur substantially faster than those of free SCN(-) and SeCN(-) ions and neutral SCN- and SeCN-derivatized molecules reported previously. This supports the N-bound configurations of MbNCS and MbNCSe, because S- and Se-bound configurations are expected to have significantly long lifetimes due to the insulation effect by heavy bridge atom like S and Se in such IR probes. Nonetheless, even though their lifetimes are much shorter than those of corresponding free ions in water, the vibrational lifetimes determined for MbNCS and MbNCSe are still fairly long compared to those of azide and cyanide myoglobin systems studied before. Thus, thiocyanate and selenocyanate can be good local probes of local electrostatic environment in the heme pocket. The globin dependence on binding mode and vibrational dynamics is also discussed.

  18. Efficient separation of transition metals from rare earths by an undiluted phosphonium thiocyanate ionic liquid.

    PubMed

    Rout, Alok; Binnemans, Koen

    2016-06-21

    The ionic liquid trihexyl(tetradecyl)phosphonium thiocyanate has been used for the extraction of the transition metal ions Co(ii), Ni(ii), Zn(ii), and the rare-earth ions La(iii), Sm(iii) and Eu(iii) from aqueous solutions containing nitrate or chloride salts. The transition metal ions showed a high affinity for the ionic liquid phase and were efficiently extracted, while the extraction efficiency of the rare-earth ions was low. This difference in extraction behavior enabled separation of the pairs Co(ii)/Sm(iii), Ni(ii)/La(iii) and Zn(ii)/Eu(iii). These separations are relevant for the recycling of rare earths and transition metals from samarium cobalt permanent magnets, nickel metal hydride batteries and lamp phosphors, respectively. The extraction of metal ions from a chloride or nitrate solution with a thiocyanate ionic liquid is an example of "split-anion extraction", where different anions are present in the aqueous and ionic liquid phase. Close to 100% loading was possible for Co(ii) and Zn(ii) up to a concentration of 40 g L(-1) of the transition metal salt in the initial aqueous feed solution, whereas the extraction efficiency for Ni(ii) gradually decreased with increase in the initial feed concentration. Stripping of Co(ii), Zn(ii) and Ni(ii) from the loaded ionic liquid phase was possible by a 15 wt% NH3 solution. The ionic liquid could reused after extraction and stripping. PMID:27243450

  19. [3,3]-sigmatropic rearrangements of fluorinated allyl (Thio)cyanates - a tool for the synthesis of fluorinated (Thio)ureas.

    PubMed

    Ramb, Daniel C; Kost, Lisa; Haufe, Günter

    2014-01-01

    The first (thio)cyanate to iso(thio)cyanate rearrangements based on 2-fluoroallylic alcohols are presented. Long-chain 2-fluoroallylic alcohols were converted to corresponding N-unsubstituted carbamates by treatment with trichloroacetyl isocyanate. Dehydration using trifluoroacetic anhydride in the presence of triethylamine formed intermediate allylic cyanates, which immediately underwent sigmatropic rearrangement to fluorinated allyl isocyanates. Without isolation the latter delivered fluorinated ureas by addition of amines. The thiocyanate to isothiocyanate rearrangements started from the same fluorinated allylic alcohols, which were first converted to mesylates. Heating in THF with potassium thiocyanate led to fluorinated allyl isothiocyanates, via [3,3]-sigmatropic rearrangement of intermediate allyl thiocyanates. The formed products were further reacted with amines to fluorinated thioureas.

  20. [3,3]-Sigmatropic shifts and retro-ene rearrangements in cyanates, isocyanates, thiocyanates, and isothiocyanates of the form RX-YCN and RX-NCY.

    PubMed

    Koch, Rainer; Finnerty, Justin J; Murali, Sukumaran; Wentrup, Curt

    2012-02-17

    Retro-ene type [2π + 2π + 2σ] and [3,3]-sigmatropic shift reactions involving the substituent groups R in heteroatom-substituted cyanates and thiocyanates RX-YCN and the isomeric isocyanates and isothiocyanates of the type RX-NCY (X = CR(2), NR', O, or S; Y = O or S) have been investigated computationally at the B3LYP/6-311++G(d,p) level. Retro-ene reactions of alkyl derivatives of the title compounds afford alkenes, imines, carbonyl and thiocarbonyl compounds together with HNCO (HNCS) or HOCN (HSCN). [3,3]-Sigmatropic shifts (hetero-Cope rearrangements) of the corresponding allyl, propargyl, benzyl, and aryl derivatives causes allylic rearrangements, propargyl-allenyl rearrangement, conversion of benzyl cyanates to o-isocyanatotoluenes, and conversion of N-cyanatoarylamines to o-isocyanatoanilines, etc. The corresponding rearrangements of allyl thiocyanates, arylamino thiocyanates and isothiocyanates, and arylsulfenyl thiocyanates and isothiocyanates are also described. PMID:22251012

  1. The use of a polymer inclusion membrane as a sorbent for online preconcentration in the flow injection determination of thiocyanate impurity in ammonium sulfate fertilizer.

    PubMed

    Ohshima, Takumi; Kagaya, Shigehiro; Gemmei-Ide, Makoto; Cattrall, Robert W; Kolev, Spas D

    2014-11-01

    A polymer inclusion membrane (PIM) is used for the first time as a sorbent in the construction of a preconcentration column to enhance the sensitivity in flow injection analysis (FIA). The PIM-coated column is readily prepared by coating the PIM containing poly(vinyl chloride), Aliquat 336, and 1-tetradecanol onto glass beads packed in a glass tube. The determination of trace amounts of thiocyanate in ammonium sulfate fertilizer demonstrates the potential of the proposed PIM-coated column in FIA. Thiocyanate standards or samples of relatively large volume (e.g. up to 2000 µL) are injected into a nitrate carrier stream. The sample zone passes through the proposed preconcentration column where thiocyanate is concentrated in a smaller volume of a carrier solution thus resulting in up to 7.4 fold increase in sensitivity. Thiocyanate is detected spectrophotometrically after its reaction with Fe(III) downstream of the preconcentration column. The limits of detection of thiocyanate in the absence and presence of 20 g L(-1) ammonium sulfate (S/N=2) are 0.014 and 0.024 mg L(-1), respectively. Thiocyanate was successfully determined in several samples of ammonium sulfate fertilizer. PMID:25127633

  2. The use of a polymer inclusion membrane as a sorbent for online preconcentration in the flow injection determination of thiocyanate impurity in ammonium sulfate fertilizer.

    PubMed

    Ohshima, Takumi; Kagaya, Shigehiro; Gemmei-Ide, Makoto; Cattrall, Robert W; Kolev, Spas D

    2014-11-01

    A polymer inclusion membrane (PIM) is used for the first time as a sorbent in the construction of a preconcentration column to enhance the sensitivity in flow injection analysis (FIA). The PIM-coated column is readily prepared by coating the PIM containing poly(vinyl chloride), Aliquat 336, and 1-tetradecanol onto glass beads packed in a glass tube. The determination of trace amounts of thiocyanate in ammonium sulfate fertilizer demonstrates the potential of the proposed PIM-coated column in FIA. Thiocyanate standards or samples of relatively large volume (e.g. up to 2000 µL) are injected into a nitrate carrier stream. The sample zone passes through the proposed preconcentration column where thiocyanate is concentrated in a smaller volume of a carrier solution thus resulting in up to 7.4 fold increase in sensitivity. Thiocyanate is detected spectrophotometrically after its reaction with Fe(III) downstream of the preconcentration column. The limits of detection of thiocyanate in the absence and presence of 20 g L(-1) ammonium sulfate (S/N=2) are 0.014 and 0.024 mg L(-1), respectively. Thiocyanate was successfully determined in several samples of ammonium sulfate fertilizer.

  3. A novel pink-pigmented facultative methylotroph, Methylobacterium thiocyanatum sp. nov., capable of growth on thiocyanate or cyanate as sole nitrogen sources.

    PubMed

    Wood, A P; Kelly, D P; McDonald, I R; Jordan, S L; Morgan, T D; Khan, S; Murrell, J C; Borodina, E

    1998-02-01

    The isolation and properties of a novel species of pink-pigmented methylotroph, Methylobacterium thiocyanatum, are described. This organism satisfied all the morphological, biochemical, and growth-substrate criteria to be placed in the genus Methylobacterium. Sequencing of the gene encoding its 16S rRNA confirmed its position in this genus, with its closest phylogenetic relatives being M. rhodesianum, M. zatmanii and M. extorquens, from which it differed in its ability to grow on several diagnostic substrates. Methanol-grown organisms contained high activities of hydroxypyruvate reductase -3 micromol NADH oxidized min-1 (mg crude extract protein)-1], showing that the serine pathway was used for methylotrophic growth. M. thiocyanatum was able to use thiocyanate or cyanate as the sole source of nitrogen for growth, and thiocyanate as the sole source of sulfur in the absence of other sulfur compounds. It tolerated high concentrations (at least 50 mM) of thiocyanate or cyanate when these were supplied as nitrogen sources. Growing cultures degraded thiocyanate to produce thiosulfate as a major sulfur end product, apparently with the intermediate formation of volatile sulfur compounds (probably hydrogen sulfide and carbonyl sulfide). Enzymatic hydrolysis of thiocyanate by cell-free extracts was not demonstrated. Cyanate was metabolized by means of a cyanase enzyme that was expressed at approximately sevenfold greater activity during growth on thiocyanate [Vmax 634 +/- 24 nmol NH3 formed min-1 (mg protein)-1] than on cyanate [89 +/- 9 nmol NH3 min-1 (mg protein)-1]. Kinetic study of the cyanase in cell-free extracts showed the enzyme (1) to exhibit high affinity for cyanate (Km 0.07 mM), (2) to require bicarbonate for activity, (3) to be subject to substrate inhibition by cyanate and competitive inhibition by thiocyanate (Ki 0.65 mM), (4) to be unaffected by 1 mM ammonium chloride, (5) to be strongly inhibited by selenocyanate, and (6) to be slightly inhibited by 5 m

  4. Ultrafast Structural Fluctuations of Myoglobin-Bound Thiocyanate and Selenocyanate Ions Measured with Two-Dimensional Infrared Photon Echo Spectroscopy.

    PubMed

    Maj, Michał; Kwak, Kyungwon; Cho, Minhaeng

    2015-11-16

    Structural dynamics within the distal cavity of myoglobin protein is investigated using 2D-IR and IR pump-probe spectroscopy of the N≡C stretch modes of heme-bound thiocyanate and selenocyanate ions. Although myoglobin-bound thiocyanate group shows a doublet in its IR absorption spectrum, no cross peaks originating from chemical exchange between the two components are observed in the time-resolved 2D IR spectra within the experimental time window. Frequency-frequency correlation functions of the two studied anionic ligands are obtained by means of a few different analysis approaches; these functions were then used to elucidate the differences in structural fluctuation around ligand, ligand-protein interactions, and the degree of structural heterogeneity within the hydrophobic pocket of these myoglobin complexes.

  5. In situ Determination of Fluoride in Groundwater Using N-Octyl Acetamide with Iron(III)-Thiocyanate Complex

    NASA Astrophysics Data System (ADS)

    Sahin, R.; Tapadia, K.; Sharma, A.

    2016-07-01

    This paper describes the nanodrop spectrophotometric determination of fluoride (F-) in a ground water sample using the organic reagent N-octylacetamide (N-OAA) with iron(III)-thiocyanate complex. The iron(III)-thiocyanate complex was extracted with a chloroform solution of amide (N-phenylacetamide, N-alkylacetamide, alkyl = butyl, phenyl, hexyl, and octyl group). This method is based upon the bleaching effect of fluoride on the red-colored extracted complex of iron(III)-thiocyanate-OAA in chloroform. The absorbance of the extract was measured pre and post F- addition at λmax = 470 nm against the reagent blank. The limit of detection and %RSD of F- was 38 μg/L and ±1.6%. The designed work followed Beer's law between 0.5 to 10 μg/mL with slope, intercept, and correlation coefficient values of -0.1101, 1.116, and -0.997, respectively. Furthermore, the applicability of the present investigation was extended for the determination of F- in a groundwater sample, and the results obtained were compared with those from another reported method.

  6. A comparative study on the aggregating effects of guanidine thiocyanate, guanidine hydrochloride and urea on lysozyme aggregation

    SciTech Connect

    Emadi, Saeed Behzadi, Maliheh

    2014-08-08

    Highlights: • Lysozyme aggregated in guanidine thiocyanate (1.0 and 2.0 M). • Lysozyme aggregated in guanidine hydrochloride (4 and 5 M). • Lysozyme did not aggregated at any concentration (0.5–5 M) of urea. • Unfolding pathway is more important than unfolding per se in aggregation. - Abstract: Protein aggregation and its subsequent deposition in different tissues culminate in a diverse range of diseases collectively known as amyloidoses. Aggregation of hen or human lysozyme depends on certain conditions, namely acidic pH or the presence of additives. In the present study, the effects on the aggregation of hen egg-white lysozyme via incubation in concentrated solutions of three different chaotropic agents namely guanidine thiocyanate, guanidine hydrochloride and urea were investigated. Here we used three different methods for the detection of the aggregates, thioflavin T fluorescence, circular dichroism spectroscopy and atomic force microscopy. Our results showed that upon incubation with different concentrations (0.5, 1.0, 2.0, 3.0, 4.0, 5.0 M) of the chemical denaturants, lysozyme was aggregated at low concentrations of guanidine thiocyanate (1.0 and 2.0 M) and at high concentrations of guanidine hydrochloride (4 and 5 M), although no fibril formation was detected. In the case of urea, no aggregation was observed at any concentration.

  7. The reevaluation of the ferric thiocyanate assay for lipid hydroperoxides with special considerations of the mechanistic aspects of the response.

    PubMed

    Mihaljević, B; Katusin-Razem, B; Razem, D

    1996-01-01

    The mechanistic aspects of the spectrophotometric method of analysis of lipid hydroperoxides (LOOH) based on the oxidation of ferrous to ferric ion and subsequent complexation of the latter by thiocyanate are considered. The method of analysis, as revised by us, was carried out in the same solvent that had been used for the extraction of lipids from the sample, a deoxygenated chloroform:methanol or a dichloromethane:methanol (2:1, v/v) mixture, and used a single solution containing both reagents, Fe2+ and SCN-, for developing the response. In that solvent, total lipids up to 5 mg/ml did not interfere, and linear increase of the absorbance of ferric thiocyanate complex was obtained up to 2 x 10(-5) M LOOH. Molar absorptivity of the ferric thiocyanate complex expressed per mol of LOOH was determined as 58,440 M-1 cm-1, based on the average of four ferric ions produced by each LOOH molecule. The estimated lowest detectable limit was about 170 pmol LOOH/ml of analyzed solution, which corresponded to about 50 mumol LOOH/kg lipid in complex natural mixtures. In addition to good sensitivity, and in contrast to some other more popular spectrophotometric assays for LOOH, the method is responsive also to hydroperoxides of mono- and di-unsaturated fatty acids. The method, thus, provides an easy, rapid, sensitive, and complete measure of hydroperoxidation of lipids. PMID:8791093

  8. Simultaneous determination of thiocyanate and salicylate by a combined UV-spectrophotometric detection principal component artificial neural network.

    PubMed

    Karimi, Hajir; Ghaedi, Mehrorang

    2006-01-01

    A modified principle component artificial neural network (PC-ANN) model is developed for simultaneous determination of thiocyanate and salycilate concentration after passing through the bulk of a liquid membrane by tri-phenyl benzyl phosphonium chloride. All calibration, and test samples data were obtained using UV-Vis spectrophotometer. In this way, a modified PC-ANN consisting of three layers of nodes was trained by combination of Bayesian-Levenberg-Marquardt as training rule. Sigmoid and liner transfer functions were used in the hidden and output layers respectively to facilitate nonlinear calibration. The model could accurately estimate the concentration of components with acceptable precision and accuracy, for mixtures. The PC-ANN model exhibits a good ability for the simultaneous determination of the thiocyanate and salycilate in concentration range 0.5 x 10(-4) mol.l(-1) up to 5.0 x 10(-4) mol.l(-1) with Root Mean square error (2.22% and 2.20%, for thiocyanate and salycilate, respectively) and high correlation coefficients (R2= 0.998 or greater). Results obtained with modified trained PC-ANN were compared with stepwise linear regression (SMLR) model. Validation of the two models shows a better ability in estimation of the modified PC-ANN as compared with the SMLR model (MSRE given are 3.12%, 6.31%.). PMID:17217170

  9. Aqueous ammonium thiocyanate solutions as refractive index-matching fluids with low density and viscosity

    NASA Astrophysics Data System (ADS)

    Morrison, Benjamin C.; Borrero-Echeverry, Daniel

    2015-11-01

    Index-matching fluids play an important role in many fluid dynamics experiments, particularly those involving particle tracking, as they can be used to minimize errors due to distortion from the refraction of light across interfaces of the apparatus. Common index-matching fluids, such as sodium iodide solutions or mineral oils, often have densities or viscosities very different from those of water. This can make them undesirable for use as a working fluid when using commercially available tracer particles or at high Reynolds numbers. A solution of ammonium thiocyanate (NH4SCN) can be used for index-matching common materials such as borosilicate glass and acrylic, and has material properties similar to those of water (ν ~ 1 . 6 cSt and ρ ~ 1 . 1 g/cc). We present an empirical model for predicting the refractive index of aqueous NH4SCN solutions as a function of temperature and NH4SCN concentration that allows experimenters to develop refractive index matching solutions for various common materials. This work was supported by the National Science Foundation (CBET-0853691) and by the James Borders Physics Student Fellowship at Reed College.

  10. Structures of Trichloromethyl Thiocyanate, CCl3 SCN, in Gaseous and Crystalline State.

    PubMed

    Berrueta Martínez, Yanina; Rodríguez Pirani, Lucas S; Erben, Mauricio F; Boese, Roland; Reuter, Christian G; Vishnevskiy, Yury V; Mitzel, Norbert W; Della Védova, Carlos O

    2016-05-18

    Trichloromethyl thiocyanate, CCl3 SCN, was structurally studied in both the gas and crystal phases by means of gas electron diffraction (GED) and single-crystal X-ray diffraction (XRD), respectively. Both experimental studies and quantum chemical calculations indicate a staggered orientation of the CCl3 group relative to the SCN group. This conclusion is supported by the similarity of the C-SCN bond length to that of the anti-structure of CH2 ClSCN (Berrueta Martínez et al. Phys. Chem. Chem. Phys. 2015, 17, 15805-15812). Bond lengths and angles are similar for gas and crystal CCl3 SCN structures; however, the crystal structure presents different intermolecular interactions. These include halogen and chalcogen type interactions, the geometry of which was studied. Characteristic C-Y⋅⋅⋅N angles (Y=Cl or S) close to 180° provide evidence for typical σ-hole interactions along the halogen/chalcogen-carbon bond in N⋅⋅⋅Cl and N⋅⋅⋅S, intermolecular units. PMID:26865044

  11. Antiinflammatory and Antimicrobial Effects of Thiocyanate in a Cystic Fibrosis Mouse Model

    PubMed Central

    Chandler, Joshua D.; Min, Elysia; Huang, Jie; McElroy, Cameron S.; Dickerhof, Nina; Mocatta, Tessa; Fletcher, Ashley A.; Evans, Christopher M.; Liang, Liping; Patel, Manisha; Kettle, Anthony J.; Nichols, David P.

    2015-01-01

    Thiocyanate (SCN) is used by the innate immune system, but less is known about its impact on inflammation and oxidative stress. Granulocytes oxidize SCN to evolve the bactericidal hypothiocyanous acid, which we previously demonstrated is metabolized by mammalian, but not bacterial, thioredoxin reductase (TrxR). There is also evidence that SCN is dysregulated in cystic fibrosis (CF), a disease marked by chronic infection and airway inflammation. To investigate antiinflammatory effects of SCN, we administered nebulized SCN or saline to β epithelial sodium channel (βENaC) mice, a phenotypic CF model. SCN significantly decreased airway neutrophil infiltrate and restored the redox ratio of glutathione in lung tissue and airway epithelial lining fluid to levels comparable to wild type. Furthermore, in Pseudomonas aeruginosa–infected βENaC and wild-type mice, SCN decreased inflammation, proinflammatory cytokines, and bacterial load. SCN also decreased airway neutrophil chemokine keratinocyte chemoattractant (also known as C-X-C motif chemokine ligand 1) and glutathione sulfonamide, a biomarker of granulocyte oxidative activity, in uninfected βENaC mice. Lung tissue TrxR activity and expression increased in inflamed lung tissue, providing in vivo evidence for the link between hypothiocyanous acid metabolism by TrxR and the promotion of selective biocide of pathogens. SCN treatment both suppressed inflammation and improved host defense, suggesting that nebulized SCN may have important therapeutic utility in diseases of both chronic airway inflammation and persistent bacterial infection, such as CF. PMID:25490247

  12. Biochemical Mechanisms and Therapeutic Potential of the Pseudohalide Thiocyanate in Human Health

    PubMed Central

    Chandler, Joshua D.; Day, Brian J.

    2016-01-01

    Thiocyanate (SCN−) is an ubiquitous molecule in mammalian biology, reaching up to mM concentrations in extracellular fluids. Two-electron oxidation of SCN− by H2O2 produces hypothiocyanous acid (HOSCN), a potent antimicrobial species. This reaction is catalyzed by chordate peroxidases (e.g., myeloperoxidase and lactoperoxidase), occurring in human secretory mucosa, including the oral cavity, airway and alimentary tract, and regulates resident and transient flora as part of innate immunity. Increasing SCN− levels limits the concentrations of a family of 2-electron oxidants (H2O2, hypohalous acids and haloamines) in favor of HOSCN formation, altering the oxidative impact on host tissue by substitution of repairable thiol and selenol oxidations instead of biomolecule degradation. This fine-tuning of inflammatory oxidation paradoxically associates with maintained host defense and decreased host injury during infections, due in part to phylogenetic differences in the thioredoxin reductase system between mammals and their pathogens. These differences could be exploited by pharmacologic use of SCN−. Recent preclinical studies have identified antimicrobial and anti-inflammatory effects of SCN− in pulmonary and cardiovascular animal models, with implications for treatment of infectious lung disease and atherogenesis. Further research is merited to expand on these findings and identify other diseases where SCN− may be of use. High oral bioavailability and an increased knowledge of the biochemical effects of SCN− on a subset of pro-inflammatory reactions suggest clinical utility. PMID:25564094

  13. Bioreactor microbial ecosystems for thiocyanate and cyanide degradation unravelled with genome-resolved metagenomics.

    PubMed

    Kantor, Rose S; van Zyl, A Wynand; van Hille, Robert P; Thomas, Brian C; Harrison, Susan T L; Banfield, Jillian F

    2015-12-01

    Gold ore processing uses cyanide (CN(-) ), which often results in large volumes of thiocyanate- (SCN(-) ) contaminated wastewater requiring treatment. Microbial communities can degrade SCN(-) and CN(-) , but little is known about their membership and metabolic potential. Microbial-based remediation strategies will benefit from an ecological understanding of organisms involved in the breakdown of SCN(-) and CN(-) into sulfur, carbon and nitrogen compounds. We performed metagenomic analysis of samples from two laboratory-scale bioreactors used to study SCN(-) and CN(-) degradation. Community analysis revealed the dominance of Thiobacillus spp., whose genomes harbour a previously unreported operon for SCN(-) degradation. Genome-based metabolic predictions suggest that a large portion of each bioreactor community is autotrophic, relying not on molasses in reactor feed but using energy gained from oxidation of sulfur compounds produced during SCN(-) degradation. Heterotrophs, including a bacterium from a previously uncharacterized phylum, compose a smaller portion of the reactor community. Predation by phage and eukaryotes is predicted to affect community dynamics. Genes for ammonium oxidation and denitrification were detected, indicating the potential for nitrogen removal, as required for complete remediation of wastewater. These findings suggest optimization strategies for reactor design, such as improved aerobic/anaerobic partitioning and elimination of organic carbon from reactor feed. PMID:26031303

  14. Bioreactor microbial ecosystems for thiocyanate and cyanide degradation unravelled with genome-resolved metagenomics.

    PubMed

    Kantor, Rose S; van Zyl, A Wynand; van Hille, Robert P; Thomas, Brian C; Harrison, Susan T L; Banfield, Jillian F

    2015-12-01

    Gold ore processing uses cyanide (CN(-) ), which often results in large volumes of thiocyanate- (SCN(-) ) contaminated wastewater requiring treatment. Microbial communities can degrade SCN(-) and CN(-) , but little is known about their membership and metabolic potential. Microbial-based remediation strategies will benefit from an ecological understanding of organisms involved in the breakdown of SCN(-) and CN(-) into sulfur, carbon and nitrogen compounds. We performed metagenomic analysis of samples from two laboratory-scale bioreactors used to study SCN(-) and CN(-) degradation. Community analysis revealed the dominance of Thiobacillus spp., whose genomes harbour a previously unreported operon for SCN(-) degradation. Genome-based metabolic predictions suggest that a large portion of each bioreactor community is autotrophic, relying not on molasses in reactor feed but using energy gained from oxidation of sulfur compounds produced during SCN(-) degradation. Heterotrophs, including a bacterium from a previously uncharacterized phylum, compose a smaller portion of the reactor community. Predation by phage and eukaryotes is predicted to affect community dynamics. Genes for ammonium oxidation and denitrification were detected, indicating the potential for nitrogen removal, as required for complete remediation of wastewater. These findings suggest optimization strategies for reactor design, such as improved aerobic/anaerobic partitioning and elimination of organic carbon from reactor feed.

  15. Paper-based analytical device for instrumental-free detection of thiocyanate in saliva as a biomarker of tobacco smoke exposure.

    PubMed

    Pena-Pereira, Francisco; Lavilla, Isela; Bendicho, Carlos

    2016-01-15

    This work describes a fast and simple assay for in situ detection of thiocyanate, i.e., a biomarker of tobacco smoke exposure, in human saliva. The assay is based on the formation of an iron(III)-thiocyanate colored complex in a paper-based sensing platform and subsequent image analysis using a scanner as detection device. Experimental parameters influencing the color intensity of the complex were fully evaluated, including the selection of detection conditions, type of paper substrate, test zone dimensions and composition as well as the stability of the paper-based device. Under optimal conditions, the detection limit was 0.06mM of thiocyanate, and the repeatability, expressed as relative standard deviation, was 3%. The proposed method, characterized by its simplicity, portability and low sample consumption, was applied to the detection of thiocyanate in a series of human saliva samples. Average thiocyanate levels in the ranges 0.28-0.87mM and 0.78-4.28mM were found for non-smokers and smokers, respectively. Recovery studies were carried out at two concentration levels, showing recovery values in the range of 96.1-103.6%.

  16. Growth, spectroscopic and physicochemical properties of bis mercury ferric chloride tetra thiocyanate: A nonlinear optical crystal

    NASA Astrophysics Data System (ADS)

    Ramesh, V.; Shihabuddeen Syed, A.; Jagannathan, K.; Rajarajan, K.

    2013-05-01

    Single crystal of bis mercury ferric chloride tetra thiocyanate [Hg2FeCl3(SCN)4; (MFCTC)] was grown from ethanol-water (3:1) mixed solvent using slow evaporation solvent technique (SEST) for the first time. The cell parameters of the grown crystal were confirmed by single crystal XRD. The coordination of transition metal ions with the SCN ligand is well-identified using FT-IR spectral analysis. The chemical composition of MFCTC was confirmed using CHNS elemental test. The ESR spectral profile of MFCTC was recorded from 298 K to 110 K, which strongly suggests the incorporation of Fe3+ ion and its environment with respect to SCN ligand. The HPLC chromatogram of MFCTC highlights the purity of the compound. The UV-Vis-NIR studies revealed the ultra violet cut-off wavelength of MFCTC in ethanol as 338 nm. The dielectric constant and dielectric loss of the sample were studied as a function of frequency and temperature. The TGA-DTA and DSC thermal analysis show that the sample is thermally stable up to 234.31 °C, which is comparatively far better than the thermal stability of Hg3CdCl2(SCN)6; (171.3 °C) and other metal-organic coordination complex crystals such as CdHg(SCN)4 (198.5 °C), Hg(N2H4CS)4Mn(SCN)4 (199.06 °C) and Hg(N2H4CS)4Zn(SCN)4 (185 °C). The SHG conversion efficiency of MFCTC is found to be higher than KDP.

  17. Mechanism and regulation of peroxidase-catalyzed nitric oxide consumption in physiological fluids: critical protective actions of ascorbate and thiocyanate.

    PubMed

    Rees, Martin D; Maiocchi, Sophie L; Kettle, Anthony J; Thomas, Shane R

    2014-07-01

    Catalytic consumption of nitric oxide (NO) by myeloperoxidase and related peroxidases is implicated as playing a key role in impairing NO bioavailability during inflammatory conditions. However, there are major gaps in our understanding of how peroxidases consume NO in physiological fluids, in which multiple reactive enzyme substrates and antioxidants are present. Notably, ascorbate has been proposed to enhance myeloperoxidase-catalyzed NO consumption by forming NO-consuming substrate radicals. However, we show that in complex biological fluids ascorbate instead plays a critical role in inhibiting NO consumption by myeloperoxidase and related peroxidases (lactoperoxidase, horseradish peroxidase) by acting as a competitive substrate for protein-bound redox intermediates and by efficiently scavenging peroxidase-derived radicals (e.g., urate radicals), yielding ascorbyl radicals that fail to consume NO. These data identify a novel mechanistic basis for how ascorbate preserves NO bioavailability during inflammation. We show that NO consumption by myeloperoxidase Compound I is significant in substrate-rich fluids and is resistant to competitive inhibition by ascorbate. However, thiocyanate effectively inhibits this process and yields hypothiocyanite at the expense of NO consumption. Hypothiocyanite can in turn form NO-consuming radicals, but thiols (albumin, glutathione) readily prevent this. Conversely, where ascorbate is absent, glutathione enhances NO consumption by urate radicals via pathways that yield S-nitrosoglutathione. Theoretical kinetic analyses provide detailed insights into the mechanisms by which ascorbate and thiocyanate exert their protective actions. We conclude that the local depletion of ascorbate and thiocyanate in inflammatory microenvironments (e.g., due to increased metabolism or dysregulated transport) will impair NO bioavailability by exacerbating peroxidase-catalyzed NO consumption.

  18. Spatial distribution of perchlorate, iodide and thiocyanate in the aquatic environment of Tianjin, China: environmental source analysis.

    PubMed

    Qin, Xiaolei; Zhang, Tao; Gan, Zhiwei; Sun, Hongwen

    2014-09-01

    Although China is the largest producer of fireworks (perchlorate-containing products) in the world, the pathways through which perchlorate enters the environment have not been characterized completely in this country. In this study, perchlorate, iodide and thiocyanate were measured in 101 water samples, including waste water, surface water, sea water and paired samples of rain water and surface runoff collected in Tianjin, China. The concentrations of the target anions were generally on the order of rain>surface water≈waste water treatment plant (WWTP) influent>WWTP effluent. High concentrations of perchlorate, iodide and thiocyanate were detected in rain samples, ranging from 0.35 to 27.3 (median: 4.05), 0.51 to 8.33 (2.92), and 1.31 to 107 (5.62) ngmL(-)(1), respectively. Furthermore, the concentrations of the target anions in rain samples were significantly (r=0.596-0.750, p<0.01) positively correlated with the concentrations obtained in the paired surface runoff samples. The anions tested showed a clear spatial distribution, and higher concentrations were observed in the upper reaches of rivers, sea waters near the coast, and rain-surface runoff pairs sampled in urban areas. Our results revealed that precipitation may act as an important source of perchlorate, iodide and thiocyanate in surface water. Moreover, iodide concentrations in the Haihe River and Dagu Drainage Canal showed a good correlation with an ideal marker (acesulfame) of domestic waste water, indicating that input from domestic waste water was an important source of iodide in the surface waters of Tianjin. PMID:24997919

  19. Spatial distribution of perchlorate, iodide and thiocyanate in the aquatic environment of Tianjin, China: environmental source analysis.

    PubMed

    Qin, Xiaolei; Zhang, Tao; Gan, Zhiwei; Sun, Hongwen

    2014-09-01

    Although China is the largest producer of fireworks (perchlorate-containing products) in the world, the pathways through which perchlorate enters the environment have not been characterized completely in this country. In this study, perchlorate, iodide and thiocyanate were measured in 101 water samples, including waste water, surface water, sea water and paired samples of rain water and surface runoff collected in Tianjin, China. The concentrations of the target anions were generally on the order of rain>surface water≈waste water treatment plant (WWTP) influent>WWTP effluent. High concentrations of perchlorate, iodide and thiocyanate were detected in rain samples, ranging from 0.35 to 27.3 (median: 4.05), 0.51 to 8.33 (2.92), and 1.31 to 107 (5.62) ngmL(-)(1), respectively. Furthermore, the concentrations of the target anions in rain samples were significantly (r=0.596-0.750, p<0.01) positively correlated with the concentrations obtained in the paired surface runoff samples. The anions tested showed a clear spatial distribution, and higher concentrations were observed in the upper reaches of rivers, sea waters near the coast, and rain-surface runoff pairs sampled in urban areas. Our results revealed that precipitation may act as an important source of perchlorate, iodide and thiocyanate in surface water. Moreover, iodide concentrations in the Haihe River and Dagu Drainage Canal showed a good correlation with an ideal marker (acesulfame) of domestic waste water, indicating that input from domestic waste water was an important source of iodide in the surface waters of Tianjin.

  20. Experimental and theoretical vibrational study of methylene bis(thiocyanate), CH2(SCN)2. A comparison with thiocyanogen, (SCN)2

    NASA Astrophysics Data System (ADS)

    Fernández, L. E.; Gómez, A. A.; Tótaro, R. M.; Coronel, A. C.; Varetti, E. L.

    2013-06-01

    The infrared and Raman spectra of methylene bis(thiocyanate), CH2(SCN)2, were obtained. The observed bands were assigned to the different normal modes of vibration using the results of a DFT calculation of the molecular vibrational properties. These results and the experimental data were used to define a Scaled Quantum Mechanics force field for the molecule. A similar treatment was applied to the thiocyanogen molecule, (SCN)2, for which the experimental frequencies were already reported in the literature. The sets of internal force constants for both molecules show very similar values.

  1. Determination of thiocyanate (biomarkers of ETS) and other inorganic ions in human nasal discharge samples using ion chromatography.

    PubMed

    Narkowicz, Sylwia; Polkowska, Żaneta; Marć, Mariusz; Simeonov, Vasil; Namieśnik, Jacek

    2013-10-01

    Environmental tobacco smoke (ETS) is a mixture of air and tobacco smoke containing more than 4000 chemical substances. In view of the health risks of many of these substances, studies are needed to determine biomarkers of exposure to ETS constituents in people who actively or passively are exposed to the toxic compounds. The methodologies for determining most biomarkers from saliva, urine and blood samples are known, but methods for analyzing these compounds in nasal discharges are not available. The objective of this work was to develop an analytical procedure for the determination of thiocyanate and other biomarker compounds in samples of nasal discharge using ion chromatography.

  2. Thyroid Antagonists (Perchlorate, Thiocyanate, and Nitrate) and Childhood Growth in a Longitudinal Study of U.S. Girls

    PubMed Central

    Mervish, Nancy A.; Pajak, Ashley; Teitelbaum, Susan L.; Pinney, Susan M.; Windham, Gayle C.; Kushi, Lawrence H.; Biro, Frank M.; Valentin-Blasini, Liza; Blount, Benjamin C.; Wolff, Mary S.

    2015-01-01

    Background: Perchlorate, thiocyanate, and nitrate are sodium/iodide symporter (NIS) inhibitors that block iodide uptake into the thyroid, thus affecting thyroid function. Thyroid dysfunction can adversely affect somatic growth and development in children. To our knowledge, no studies have examined effects of NIS inhibitors on body size measures. Objective: We investigated associations between NIS inhibitors and childhood growth in 940 girls from the Puberty Study of the Breast Cancer and Environment Research Program. Methods: Urine samples collected from girls 6–8 years of age at enrollment (2004–2007) from New York City, greater Cincinnati, Ohio, and the Bay Area in California were analyzed for NIS inhibitors and creatinine (C). The longitudinal association between NIS inhibitors and anthropometric measures [height, waist circumference, and body mass index (BMI)] during at least three visits was examined using mixed effects linear models, adjusted for race and site. Results: Compared with girls in the low-exposure group (3.6, 626, and 500 mg/gC, median perchlorate, thiocyanate, and nitrate, respectively) girls with the highest NIS inhibitor exposure (9.6, 2,343, and 955 mg/gC, median perchlorate, thiocyanate, and nitrate, respectively) had slower growth in waist circumference and BMI but not height. Significant differences in the predicted mean waist circumference and BMI between the low- and high-exposure groups were observed beginning at 11 years of age. Conclusions: Higher NIS inhibitor exposure biomarkers were associated with reductions in waist circumference and BMI. These findings underscore the need to assess exposure to NIS inhibitors with respect to their influence on childhood growth. Citation: Mervish NA, Pajak A, Teitelbaum SL, Pinney SM, Windham GC, Kushi LH, Biro FM, Valentin-Blasini L, Blount BC, Wolff MS, for the Breast Cancer and Environment Research Project (BCERP). 2016. Thyroid antagonists (perchlorate, thiocyanate, and nitrate) and

  3. Combined Effects of Perchlorate, Thiocyanate, and Iodine on Thyroid Function in the National Health and Nutrition Examination Survey 2007-8

    PubMed Central

    Steinmaus, Craig; Miller, Mark D.; Cushing, Lara; Blount, Benjamin C.; Smith, Allan H.

    2013-01-01

    Perchlorate, thiocyanate, and low iodine intake can all decrease iodide intake into the thyroid gland. This can reduce thyroid hormone production since iodide is a key component of thyroid hormone. Previous research has suggested that each of these factors alone may decrease thyroid hormone levels, but effect sizes are small. We hypothesized that people who have all three factors at the same time have substantially lower thyroid hormone levels than people who do not, and the effect of this combined exposure is substantially larger than the effects seen in analyses focused on only one factor at a time. Using data from the 2007-2008 National Health and Nutrition Examination Survey, subjects were categorized into exposure groups based on their urinary perchlorate, iodine, and thiocyanate concentrations, and mean serum thyroxine concentrations were compared between groups. Subjects with high perchlorate (n=1939) had thyroxine concentrations that were 5.0% lower (mean difference = 0.40 µg/dl, 95% confidence interval=0.14-0.65) than subjects with low perchlorate (n=2084). The individual effects of iodine and thiocyanate were even smaller. Subjects with high perchlorate, high thiocyanate, and low iodine combined (n=62) had thyroxine concentrations 12.9% lower (mean difference = 1.07 µg/dl, 95% confidence interval=0.55-1.59) than subjects with low perchlorate, low thiocyanate, and adequate iodine (n=376). Potential confounders had little impact on results. Overall, these results suggest that concomitant exposure to perchlorate, thiocyanate, and low iodine markedly reduces thyroxine production. This highlights the potential importance of examining the combined effects of multiple agents when evaluating the toxicity of thyroid-disrupting agents. PMID:23473920

  4. Combined effects of perchlorate, thiocyanate, and iodine on thyroid function in the National Health and Nutrition Examination Survey 2007–08

    SciTech Connect

    Steinmaus, Craig; Miller, Mark D.; Cushing, Lara; Blount, Benjamin C.; Smith, Allan H.

    2013-05-15

    Perchlorate, thiocyanate, and low iodine intake can all decrease iodide intake into the thyroid gland. This can reduce thyroid hormone production since iodide is a key component of thyroid hormone. Previous research has suggested that each of these factors alone may decrease thyroid hormone levels, but effect sizes are small. We hypothesized that people who have all three factors at the same time have substantially lower thyroid hormone levels than people who do not, and the effect of this combined exposure is substantially larger than the effects seen in analyses focused on only one factor at a time. Using data from the 2007–2008 National Health and Nutrition Examination Survey, subjects were categorized into exposure groups based on their urinary perchlorate, iodine, and thiocyanate concentrations, and mean serum thyroxine concentrations were compared between groups. Subjects with high perchlorate (n=1939) had thyroxine concentrations that were 5.0% lower (mean difference=0.40 μg/dl, 95% confidence interval=0.14–0.65) than subjects with low perchlorate (n=2084). The individual effects of iodine and thiocyanate were even smaller. Subjects with high perchlorate, high thiocyanate, and low iodine combined (n=62) had thyroxine concentrations 12.9% lower (mean difference=1.07 μg/dl, 95% confidence interval=0.55–1.59) than subjects with low perchlorate, low thiocyanate, and adequate iodine (n=376). Potential confounders had little impact on results. Overall, these results suggest that concomitant exposure to perchlorate, thiocyanate, and low iodine markedly reduces thyroxine production. This highlights the potential importance of examining the combined effects of multiple agents when evaluating the toxicity of thyroid-disrupting agents. -- Highlights: ► Recent data suggest that essentially everyone in the US is exposed to perchlorate. ► Perchlorate exposure may be associated with lower thyroid hormone levels. ► Some groups may be more susceptible to

  5. Cloning of Genes Coding for the Three Subunits of Thiocyanate Hydrolase of Thiobacillus thioparus THI 115 and Their Evolutionary Relationships to Nitrile Hydratase

    PubMed Central

    Katayama, Yoko; Matsushita, Yasuhiko; Kaneko, Miyuki; Kondo, Mai; Mizuno, Tadayoshi; Nyunoya, Hiroshi

    1998-01-01

    Thiocyanate hydrolase is a newly found enzyme from Thiobacillus thioparus THI 115 that converts thiocyanate to carbonyl sulfide and ammonia (Y. Katayama, Y. Narahara, Y. Inoue, F. Amano, T. Kanagawa, and H. Kuraishi, J. Biol. Chem. 267:9170–9175, 1992). We have cloned and sequenced the scn genes that encode the three subunits of the enzyme. The scnB, scnA, and scnC genes, arrayed in this order, contained open reading frames encoding sequences of 157, 126, and 243 amino acid residues, respectively, for the β, α, and γ subunits, respectively. Each open reading frame was preceded by a typical Shine-Dalgarno sequence. The deduced amino-terminal peptide sequences for the three subunits were in fair agreement with the chemically determined sequences. The protein molecular mass calculated for each subunit was compatible with that determined by sodium dodecyl sulfate-polyacrylamide gel electrophoresis. From a computer analysis, thiocyanate hydrolase showed significant homologies to bacterial nitrile hydratases known to convert nitrile to the corresponding amide, which is further hydrolyzed by amidase to form acid and ammonia. The two enzymes were homologous over regions corresponding to almost the entire coding regions of the genes: the β and α subunits of thiocyanate hydrolase were homologous to the amino- and carboxyl-terminal halves of the β subunit of nitrile hydratase, and the γ subunit of thiocyanate hydrolase was homologous to the α subunit of nitrile hydratase. Comparisons of the catalytic properties of the two homologous enzymes support the model for the reaction steps of thiocyanate hydrolase that was previously presented on the basis of biochemical analyses. PMID:9573140

  6. Oxygen-18 study of the mechanism of promoter action of thiocyanate ions in the electrosynthesis of persulfuric acid and ammonium persulfate at platinum anodes

    SciTech Connect

    Kasatkin, E.V.; Larchenko, L.I.; Potapova, G.F.

    1987-02-01

    The authors use labelled oxygen to study the involvement of water and sulfate ions in molecular oxygen evolution during the anodic synthesis of persulfuric acid and ammonium persulfate at a platinum anode in an electrolytic cell with and without thiocyanate as a promoter for the electrocatalytic reaction.

  7. A one-dimensional CdII coordination polymer constructed from 4-(dimethylamino)pyridinium-1-acetate ligands and thiocyanate coordination bridges.

    PubMed

    Wang, Hui-Ting; Zhou, Lin

    2015-07-01

    A new cadmium-thiocyanate complex, namely catena-poly[1-carboxymethyl-4-(dimethylamino)pyridinium [cadmium(II)-tri-μ-thiocyanato-κ(4)N:S;κ(2)S:N] [[[4-(dimethylamino)pyridinium-1-acetate-κ(2)O,O']cadmium(II)]-di-μ-thiocyanato-κ(2)N:S;κ(2)S:N

  8. Conditional pharmacology/toxicology V: ambivalent effects of thiocyanate upon the development and the inhibition of experimental arthritis in rats by aurothiomalate (Myocrysin®) and metallic silver.

    PubMed

    Whitehouse, Michael; Butters, Desley; Vernon-Roberts, Barrie

    2013-08-01

    This article discusses the bizarre and contrary effects of thiocyanate, the major detoxication product of hydrogen cyanide inhaled from tobacco smoke or liberated from cyanogenic foods, e.g. cassava. Thiocyanate both (1) promotes inflammatory disease in rats and (2) facilitates the anti-inflammatory action of historic metal therapies based on gold (Au) or silver (Ag) in three models of chronic polyarthritis in rats. Low doses of nanoparticulate metallic silver (NMS) preparations, i.e. zerovalent silver (Ag°) administered orally, suppressed the mycobacterial ('adjuvant')-induced arthritis (MIA) in rats. Similar doses of cationic silver, Ag(I), administered orally as silver oxide or soluble silver salts were inactive. By contrast, NMS only inhibited the development of the collagen-induced arthritis (CIA) and pristane-induced arthritis (PIA) in rats when thiocyanate was also co-administered in drinking water. These (a) arthritis-selective and (b) thiocyanate-inducible effects of Ag° were also observed in some previous, and now extended, studies with the classic anti-arthritic drug, sodium aurothiomalate (ATM, Myocrisin(®)) and its silver analogue (STM), administered subcutaneously to rats developing the same three forms of polyarthritis. In the absence of either Ag° or ATM, thiocyanate considerably increased the severity of the MIA, CIA and PIA, i.e. acting as a pro-pathogen. Hitherto, thiocyanate was considered relatively harmless. This may not be true in rats/people with immuno-inflammatory stress and concomitant leukocyte activation. Collectively, these findings show how the drug action of a xenobiotic might be determined by the nature (and severity) of the experimental inflammation, as an example of conditional pharmacology. They also suggest that an incipient toxicity, even of normobiotics such as thiocyanate, might likewise be modulated beneficially by well-chosen xenobiotics (drugs, nutritional supplements, etc.), i.e. conditional toxicology (Powanda 1995

  9. Thiocyanate-Capped Nanocrystal Colloids: Vibrational Reporter of Surface Chemistry and Solution-Based Route to Enhanced Coupling in Nanocrystal Solids

    SciTech Connect

    Fafarman, AT; Koh, WK; Diroll, BT; Kim, DK; Ko, DK; Oh, SJ; Ye, XC; Doan-Nguyen, V; Crump, MR; Reifsnyder, DC; Murray, CB; Kagan, CR

    2011-10-05

    Ammonium thiocyanate (NH(4)SCN) is introduced to exchange the long, insulating ligands used in colloidal nanocrystal (NC) synthesis. The short, air-stable, environmentally benign thiocyanate ligand electrostatically stabilizes a variety of semiconductor and metallic NCs in polar solvents, allowing solution-based deposition of NCs into thin-film NC solids. NH(4)SCN is also effective in replacing ligands on NCs after their assembly into the solid state. The spectroscopic properties of this ligand provide unprecedented insight into the chemical and electronic nature of the surface of the NCs. Spectra indicate that the thiocyanate binds to metal sites on the NC surface and is sensitive to atom type and NC surface charge. The short, thiocyanate ligand gives rise to significantly enhanced electronic coupling between NCs as evidenced by large bathochromic shifts in the absorption spectra of CdSe and CdTe NC thin films and by conductivities as high as (2 +/- 0.7) x 10(3) Omega(-1) cm(-1) for Au NC thin films deposited from solution. NH(4)SCN treatment of PbTe NC films increases the conductivity by 10(13), allowing the first Hall measurements of nonsintered NC solids, with Hall effect mobilities of 2.8 +/- 0.7 cm(2)/(V.s). Thiocyanate-capped CdSe NC thin films form photodetectors exhibiting sensitive photoconductivity of 10(-5) Omega(-1) cm(-1) under 30 mW/cm(2) of 488 nm illumination with I(photo)/I(dark) > 10(3) and form n-channel thin-film transistors with electron mobilities of 1.5 +/- 0.7 cm(2)/(V.s), a current modulation of >10(6), and a subthreshold swing of 0.73 V/decade.

  10. Thiocyanate-capped nanocrystal colloids: vibrational reporter of surface chemistry and solution-based route to enhanced coupling in nanocrystal solids.

    PubMed

    Fafarman, Aaron T; Koh, Weon-kyu; Diroll, Benjamin T; Kim, David K; Ko, Dong-Kyun; Oh, Soong Ju; Ye, Xingchen; Doan-Nguyen, Vicky; Crump, Michael R; Reifsnyder, Danielle C; Murray, Christopher B; Kagan, Cherie R

    2011-10-01

    Ammonium thiocyanate (NH(4)SCN) is introduced to exchange the long, insulating ligands used in colloidal nanocrystal (NC) synthesis. The short, air-stable, environmentally benign thiocyanate ligand electrostatically stabilizes a variety of semiconductor and metallic NCs in polar solvents, allowing solution-based deposition of NCs into thin-film NC solids. NH(4)SCN is also effective in replacing ligands on NCs after their assembly into the solid state. The spectroscopic properties of this ligand provide unprecedented insight into the chemical and electronic nature of the surface of the NCs. Spectra indicate that the thiocyanate binds to metal sites on the NC surface and is sensitive to atom type and NC surface charge. The short, thiocyanate ligand gives rise to significantly enhanced electronic coupling between NCs as evidenced by large bathochromic shifts in the absorption spectra of CdSe and CdTe NC thin films and by conductivities as high as (2 ± 0.7) × 10(3) Ω(-1) cm(-1) for Au NC thin films deposited from solution. NH(4)SCN treatment of PbTe NC films increases the conductivity by 10(13), allowing the first Hall measurements of nonsintered NC solids, with Hall effect mobilities of 2.8 ± 0.7 cm(2)/(V·s). Thiocyanate-capped CdSe NC thin films form photodetectors exhibiting sensitive photoconductivity of 10(-5) Ω(-1) cm(-1) under 30 mW/cm(2) of 488 nm illumination with I(photo)/I(dark) > 10(3) and form n-channel thin-film transistors with electron mobilities of 1.5 ± 0.7 cm(2)/(V·s), a current modulation of >10(6), and a subthreshold swing of 0.73 V/decade.

  11. New approach to optimize operational conditions for the biological treatment of a high-strength thiocyanate and ammonium waste: pH as key factor.

    PubMed

    Lay-Son, Meiling; Drakides, Christian

    2008-02-01

    Biological treatment of coke and steel-processing wastewaters has to satisfy both industrial economic needs and environmental protection regulations. Nevertheless, as some of the pollutants contained in these waters or produced during the treatment are highly toxic, an effective and safe treatment has proved to be difficult to obtain. This paper reports the study of a biological method for the treatment of wastewaters containing free cyanide, thiocyanate and ammonium (NH4). Laboratory-scale activated-sludge reactors were fed with a synthetic solution reproducing a steel-processing industrial wastewater and inoculated with the same industrial bacterial seeding used on-site (Ecosynergie Inc.). The results demonstrated that free cyanide and thiocyanate were efficiently degraded. Nevertheless, thiocyanate degradation and nitrification processes were actually inhibited by the free ammonia form (NH3) in place of the ionized NH4 form (NH4+) currently dosed and often unproperly named "ammonia" [IUPAC, 1997. In: McNaught, A.D., Wilkinson, A. (compilers). Compendium of Chemical Terminology. Royal Society of Chemistry, Cambridge, UK]. Optimum degradation rates were obtained for very narrow ranges of ammonia nitrogen (NH3-N) concentrations. This result can be explained by the role of pH, which mainly controls the NH3/NH4 equilibrium. Pollutants and NH3 concentrations influenced degradation rates of main pollutants. This influence was determined and expressed through elementary equations. Although the Michaelis-Menten equation could have been used to describe thiocyanate degradation, a Haldane-inhibition model was used to satisfactorily describe cyanide degradation. On the other hand, a slightly modified Haldane model was applied to describe both NH4 oxidation using NH3-N as substrate and thiocyanate degradation using NH3-N as inhibitor. These findings emphasize the role of pH on degradation rates and allow one to optimize operational conditions in the biological treatment of

  12. Probing the early stages of salt nucleation—Experimental and theoretical investigations of sodium/potassium thiocyanate cluster anions

    NASA Astrophysics Data System (ADS)

    Deng, S. H. M.; Kong, Xiang-Yu; Wang, Xue-Bin

    2015-01-01

    Due to the fast solvent evaporation in electrospray ionization (ESI), the concentration of initially dilute electrolyte solutions rapidly increases to afford the formation of supersaturated droplets and generation of various pristine anhydrous salt clusters in the gas phase. The size, composition, and charge distributions of these clusters, in principle, witness the nucleation evolution in solutions. Herein, we report a microscopic study on the initial stage of nucleation and crystallization of sodium/potassium thiocyanate salt solutions simulated in the ESI process. Singly charged M x (SCN)x + 1 - , doubly charged M y (SCN)y + 2 2 - (M = Na, K), and triply charged K z (SCN)z + 3 3 - anion clusters (x, y, and z stand for the number of alkali atoms in the singly, doubly, and triply charged clusters, respectively) were produced via electrospray of the corresponding salt solutions and were characterized by negative ion photoelectron spectroscopy (NIPES). The vertical detachment energies (VDEs) of these sodium/potassium thiocyanate cluster anions were obtained, and theoretical calculations were carried out for the sodium thiocyanate clusters in assisting spectral identification. The measured VDEs of singly charged anions M x (SCN)x + 1 - (M = Na and K) demonstrate that they are superhalogen anions. The existence of doubly charged anions M y (SCN)y + 2 2 - (y = 2x, x ≥ 4 and 3 for M = Na and K, respectively) and triply charged anions K z (SCN)z + 3 3 - (z = 3x, x ≥ 6) was initially discovered from the photoelectron spectra for those singly charged anions of M x (SCN)x + 1 - with the same mass-to-charge ratio (m/z), and later independently confirmed by the observation of their distinct mass spectral distributions and by taking their NIPE spectra for those pure multiply charged anions with their m/z different from the singly charged species. For large clusters, multiply charged clusters were found to become preferred, but at higher temperatures, those multiply charged

  13. Probing the early stages of salt nucleation--experimental and theoretical investigations of sodium/potassium thiocyanate cluster anions.

    PubMed

    Deng, S H M; Kong, Xiang-Yu; Wang, Xue-Bin

    2015-01-14

    Due to the fast solvent evaporation in electrospray ionization (ESI), the concentration of initially dilute electrolyte solutions rapidly increases to afford the formation of supersaturated droplets and generation of various pristine anhydrous salt clusters in the gas phase. The size, composition, and charge distributions of these clusters, in principle, witness the nucleation evolution in solutions. Herein, we report a microscopic study on the initial stage of nucleation and crystallization of sodium/potassium thiocyanate salt solutions simulated in the ESI process. Singly charged Mx(SCN)x+1(-), doubly charged My(SCN)y+2(2-) (M = Na, K), and triply charged Kz(SCN)z+3(3-) anion clusters (x, y, and z stand for the number of alkali atoms in the singly, doubly, and triply charged clusters, respectively) were produced via electrospray of the corresponding salt solutions and were characterized by negative ion photoelectron spectroscopy (NIPES). The vertical detachment energies (VDEs) of these sodium/potassium thiocyanate cluster anions were obtained, and theoretical calculations were carried out for the sodium thiocyanate clusters in assisting spectral identification. The measured VDEs of singly charged anions Mx(SCN)x+1(-) (M = Na and K) demonstrate that they are superhalogen anions. The existence of doubly charged anions My(SCN)y+2(2-) (y = 2x, x ≥ 4 and 3 for M = Na and K, respectively) and triply charged anions Kz(SCN)z+3(3-) (z = 3x, x ≥ 6) was initially discovered from the photoelectron spectra for those singly charged anions of Mx(SCN)x+1(-) with the same mass-to-charge ratio (m/z), and later independently confirmed by the observation of their distinct mass spectral distributions and by taking their NIPE spectra for those pure multiply charged anions with their m/z different from the singly charged species. For large clusters, multiply charged clusters were found to become preferred, but at higher temperatures, those multiply charged clusters were suppressed

  14. Probing the early stages of salt nucleation—experimental and theoretical investigations of sodium/potassium thiocyanate cluster anions

    SciTech Connect

    Deng, Shihu; Kong, Xiangyu; Wang, Xue B.

    2015-01-14

    Due to fast solvent evaporation in electrospray ionization (ESI), the concentration of initially dilute electrolyte solutions rapidly increases to afford formation of supersaturated droplets and generating various pristine anhydrous salt clusters in the gas phase. The size, composition, and charge distributions of these clusters, in principle witness the nucleation evolution in solutions. Herein, we report a microscopic study on the initial stage of nucleation and crystallization of sodium/potassium thiocyanate salt solutions simulated in the ESI process. Singly charged Mx(SCN)⁻x+1, doubly charged My(SCN)²⁻y+2 (M = Na, K), and triply charged Kz(SCN)³⁻z+3 anion clusters were produced via electrospray of the corresponding salt solutions, and were characterized by negative ion photoelectron spectroscopy (NIPES). The vertical detachment energies (VDEs) of these sodium/potassium thiocyanate cluster anions were obtained, and theoretical calculations were carried out for sodium thiocyanate clusters in assisting spectral identification. The measured VDEs of singly charged anions Mx(SCN)⁻x+1 (M = Na and K) demonstrate they are superhalogen anions. The existence of doubly charged anions My (SCN)²⁻y+2 (y = 2x, x ≥ 4 and 3 for M = Na and K, respectively) and triply charged anions Kz(SCN)³⁻z+3 (z = 3x, x ≥ 6) were initially discovered from the photoelectron spectra for those singly charged anions of Msub>x(SCN)⁻x+1 with the same mass-to-charge ratio (m/z), and later independently confirmed by observation of their distinct mass spectral distributions and by taking their NIPE spectra for those pure multiply charged anions with their m/z different from the singly charged species. For large clusters, multiply charged clusters are found to become preferred, but at higher temperatures those multiply charged clusters

  15. Probing the early stages of salt nucleation—Experimental and theoretical investigations of sodium/potassium thiocyanate cluster anions

    SciTech Connect

    Deng, S. H. M.; Kong, Xiang-Yu; Wang, Xue-Bin

    2015-01-14

    Due to the fast solvent evaporation in electrospray ionization (ESI), the concentration of initially dilute electrolyte solutions rapidly increases to afford the formation of supersaturated droplets and generation of various pristine anhydrous salt clusters in the gas phase. The size, composition, and charge distributions of these clusters, in principle, witness the nucleation evolution in solutions. Herein, we report a microscopic study on the initial stage of nucleation and crystallization of sodium/potassium thiocyanate salt solutions simulated in the ESI process. Singly charged M{sub x}(SCN){sub x+1}{sup −}, doubly charged M{sub y}(SCN){sub y+2}{sup 2−} (M = Na, K), and triply charged K{sub z}(SCN){sub z+3}{sup 3−} anion clusters (x, y, and z stand for the number of alkali atoms in the singly, doubly, and triply charged clusters, respectively) were produced via electrospray of the corresponding salt solutions and were characterized by negative ion photoelectron spectroscopy (NIPES). The vertical detachment energies (VDEs) of these sodium/potassium thiocyanate cluster anions were obtained, and theoretical calculations were carried out for the sodium thiocyanate clusters in assisting spectral identification. The measured VDEs of singly charged anions M{sub x}(SCN){sub x+1}{sup −} (M = Na and K) demonstrate that they are superhalogen anions. The existence of doubly charged anions M{sub y}(SCN){sub y+2}{sup 2−} (y = 2x, x ≥ 4 and 3 for M = Na and K, respectively) and triply charged anions K{sub z}(SCN){sub z+3}{sup 3−} (z = 3x, x ≥ 6) was initially discovered from the photoelectron spectra for those singly charged anions of M{sub x}(SCN){sub x+1}{sup −} with the same mass-to-charge ratio (m/z), and later independently confirmed by the observation of their distinct mass spectral distributions and by taking their NIPE spectra for those pure multiply charged anions with their m/z different from the singly charged species. For large clusters, multiply

  16. A comprehensive study on algal-bacterial communities shift during thiocyanate degradation in a microalga-mediated process.

    PubMed

    Ryu, Byung-Gon; Kim, Woong; Nam, Kibok; Kim, Sungwhan; Lee, Bongsoo; Park, Min S; Yang, Ji-Won

    2015-09-01

    Changes in algal and bacterial communities during thiocyanate (SCN(-)) decomposition in a microalga-mediated process were studied. Pyrosequencing indicated that Thiobacillus bacteria and Micractinium algae predominated during SCN(-) hydrolysis, even after its complete degradation. Principal components analysis and evenness profiles (based on the Pareto-Lorenz curve) suggested that the changes in the bacterial communities were driven by nitrogen and sulfur oxidation, pH changes, and photoautotrophic conditions. The populations of predominant microalgae remained relatively stable during SCN(-) hydrolysis, but the proportion of bacteria - especially nitrifying bacteria - fluctuated. Thus, the initial microalgal population may be crucial in determining which microorganisms dominate when the preferred nitrogen source becomes limited. The results also demonstrated that microalgae and SCN(-)-hydrolyzing bacteria can coexist, that microalgae can be effectively used with these bacteria to completely treat SCN(-), and that the structure of the algal-bacterial community is more stable than the community of nitrifying bacteria alone during SCN(-) degradation.

  17. Chronic toxicity of erythromycin thiocyanate to Daphnia magna in a flow-through, continuous exposure test system

    USGS Publications Warehouse

    Meinertz, J.R.; Schreier, T.M.; Bernardy, J.A.

    2011-01-01

    Approval of a new animal drug application for AQUAMYCIN 100?? (erythromycin thiocyanate; ET) to treat freshwater salmonid species with bacterial kidney disease is being pursued in the US. As part of the approval process, ETs impact on an aquatic environment had to be described in an environmental assessment. The environmental assessment was lacking data to characterize the effect ET would have on a chronically exposed aquatic invertebrate organism. A major step to fulfilling the environmental assessment was completed after conducting a comprehensive study continuously exposing Daphnia magna to ET for 21 days. Results indicated that the no observable effect concentration for ET was 179 ??g/L. ?? 2011 Springer Science+Business Media, LLC (outside the USA).

  18. Chronic toxicity of diphenhydramine hydrochloride and erythromycin thiocyanate to Daphnia, Daphnia magna, in a continuous exposure test system

    USGS Publications Warehouse

    Meinertz, J.R.; Schreier, T.M.; Bernardy, J.A.; Franz, J.L.

    2010-01-01

    Diphenhydramine hydrochloride (DH; Benadryl TM, an over-the-counter antihistamine) and erythromycin thiocyanate (ET; a commonly used macrolide antibiotic) are pharmaceutical compounds whose chronic toxicity to Daphnia magna had not been characterized. Continuous exposure to DH concentrations about 5 times greater than the maximum reported environmental concentration of 0.023 lg/L for 21 days or to ET concentrations about 40 times the maximum reported environmental concentration of 6 (mu or u)g/L for 21 days did not significantly impact D. magna survival and production. In this study the no observable effect concentration for DH was 0.12 (mu or u)g/L and for ET was 248 (mu or u)g/L.

  19. A comprehensive study on algal-bacterial communities shift during thiocyanate degradation in a microalga-mediated process.

    PubMed

    Ryu, Byung-Gon; Kim, Woong; Nam, Kibok; Kim, Sungwhan; Lee, Bongsoo; Park, Min S; Yang, Ji-Won

    2015-09-01

    Changes in algal and bacterial communities during thiocyanate (SCN(-)) decomposition in a microalga-mediated process were studied. Pyrosequencing indicated that Thiobacillus bacteria and Micractinium algae predominated during SCN(-) hydrolysis, even after its complete degradation. Principal components analysis and evenness profiles (based on the Pareto-Lorenz curve) suggested that the changes in the bacterial communities were driven by nitrogen and sulfur oxidation, pH changes, and photoautotrophic conditions. The populations of predominant microalgae remained relatively stable during SCN(-) hydrolysis, but the proportion of bacteria - especially nitrifying bacteria - fluctuated. Thus, the initial microalgal population may be crucial in determining which microorganisms dominate when the preferred nitrogen source becomes limited. The results also demonstrated that microalgae and SCN(-)-hydrolyzing bacteria can coexist, that microalgae can be effectively used with these bacteria to completely treat SCN(-), and that the structure of the algal-bacterial community is more stable than the community of nitrifying bacteria alone during SCN(-) degradation. PMID:25911193

  20. Microbially-mediated thiocyanate oxidation and manganese cycling control arsenic mobility in groundwater at an Australian gold mine

    NASA Astrophysics Data System (ADS)

    Horvath, A. S.; Baldisimo, J. G.; Moreau, J. W.

    2010-12-01

    Arsenic contamination of groundwater poses a serious environmental and human health problem in many regions around the world. Historical groundwater chemistry data for a Western-Central Victorian gold mine (Australia) revealed a strong inverse correlation between dissolved thiocyanate and iron(II), supporting the interpretation that oxidation of thiocyanate, a major groundwater contaminant by-product of cyanide-based gold leaching, was coupled to reductive dissolution of iron ox(yhydrox)ides in tailings dam sediments. Microbial growth was observed in this study in a selective medium using SCN- as the sole carbon and nitrogen source. The potential for use of SCN- as a tracer of mining contamination in groundwater was evaluated in the context of biological SCN- oxidation potential in the aquifer. Geochemical data also revealed a high positive correlation between dissolved arsenic and manganese, indicating that sorption on manganese-oxides most likely controls arsenic mobility at this site. Samples of groundwater and sediments along a roughly straight SW-NE traverse away from a large mine tailings storage facility, and parallel to the major groundwater flow direction, were analysed for major ions and trace metals. Groundwater from wells approaching the tailings along this traverse showed a nearly five-fold increase (roughly 25-125 ppb) in dissolved arsenic concentrations relative to aqueous Mn(II) concentrations. Thus, equivalent amounts of dissolved manganese released a five-fold difference in the amount of adsorbed arsenic. The interpretation that reductive dissolution of As-bearing MnO2 at the mine site has been mediated by groundwater (or aquifer) microorganisms is consistent with our recovery of synthetic birnessite-reducing enrichment cultures that were inoculated with As-contaminated groundwaters.

  1. Cyanide toxicokinetics: the behavior of cyanide, thiocyanate and 2-amino-2-thiazoline-4-carboxylic acid in multiple animal models.

    PubMed

    Bhandari, Raj K; Oda, Robert P; Petrikovics, Ilona; Thompson, David E; Brenner, Matthew; Mahon, Sari B; Bebarta, Vikhyat S; Rockwood, Gary A; Logue, Brian A

    2014-05-01

    Cyanide causes toxic effects by inhibiting cytochrome c oxidase, resulting in cellular hypoxia and cytotoxic anoxia, and can eventually lead to death. Cyanide exposure can be verified by direct analysis of cyanide concentrations or analyzing its metabolites, including thiocyanate (SCN(-)) and 2-amino-2-thiazoline-4-carboxylic acid (ATCA) in blood. To determine the behavior of these markers following cyanide exposure, a toxicokinetics study was performed in three animal models: (i) rats (250-300 g), (ii) rabbits (3.5-4.2 kg) and (iii) swine (47-54 kg). Cyanide reached a maximum in blood and declined rapidly in each animal model as it was absorbed, distributed, metabolized and eliminated. Thiocyanate concentrations rose more slowly as cyanide was enzymatically converted to SCN(-). Concentrations of ATCA did not rise significantly above the baseline in the rat model, but rose quickly in rabbits (up to a 40-fold increase) and swine (up to a 3-fold increase) and then fell rapidly, generally following the relative behavior of cyanide. Rats were administered cyanide subcutaneously and the apparent half-life (t1/2) was determined to be 1,510 min. Rabbits were administered cyanide intravenously and the t1/2 was determined to be 177 min. Swine were administered cyanide intravenously and the t1/2 was determined to be 26.9 min. The SCN(-) t1/2 in rats was 3,010 min, but was not calculated in rabbits and swine because SCN(-) concentrations did not reach a maximum. The t1/2 of ATCA was 40.7 and 13.9 min in rabbits and swine, respectively, while it could not be determined in rats with confidence. The current study suggests that cyanide exposure may be verified shortly after exposure by determining significantly elevated cyanide and SCN(-) in each animal model and ATCA may be used when the ATCA detoxification pathway is significant.

  2. A two-dimensional cadmium(II) coordination polymer based on 1-cyanomethyl-4-aza-1-azoniabicyclo[2.2.2]octane and thiocyanate ligands.

    PubMed

    Wang, Hui-Ting; Li, Qiang; Zhou, Lin

    2015-09-01

    A cadmium-thiocyanate complex, poly[(1-cyanomethyl-4-aza-1-azoniabicyclo[2.2.2]octane-κ(4)N)octakis-μ2-thiocyanato-κ(8)N:S;κ(8)S:N-tricadmium(II)], [Cd3(C8H14N3)2(NCS)8]n, was synthesized by the reaction of 1-cyanomethyl-4-aza-1-azoniabicyclo[2.2.2]octane chloride, cadmium nitrate tetrahydrate and potassium thiocyanide in aqueous solution. In the crystal structure, there are two independent types of Cd(II) cation (one on a centre of inversion and one in a general position) and both are in distorted octahedral coordination environments, coordinated by N and S atoms from different ligands. Neighbouring Cd(II) cations are linked together by thiocyanate bridges to form a two-dimensional network. Hydrogen-bonding interactions are involved in the formation of a three-dimensional supramolecular network.

  3. Impact of Smoking and Thiocyanate on Perchlorate and Thyroid Hormone Associations in the 2001–2002 National Health and Nutrition Examination Survey

    PubMed Central

    Steinmaus, Craig; Miller, Mark D.; Howd, Robert

    2007-01-01

    Background Findings from a recent large study suggest that perchlorate at commonly occurring exposure concentrations may decrease thyroid hormone levels in some women. Decreases in thyroid hormone seen with perchlorate exposure could be even greater in people with concomitant exposure to agents such as thiocyanate that may affect the thyroid by mechanisms similar to those of perchlorate. Objectives and methods We used data from the National Health and Nutrition Examination Survey to assess the impact of smoking and thiocyanate on the relationship between urinary per-chlorate and serum thyroxine (T4) and thyroid-stimulating hormone (TSH). Results In women with urinary iodine levels < 100 μg/L, the association between the logarithm of perchlorate and decreased T4 was greater in smokers [regression coefficient (β) = −1.66, p = 0.0005] than in nonsmokers (β = −0.54, p = 0.04). In subjects with high, medium, and low cotinine levels, these regression coefficients were −1.47 (p = 0.0002), −0.57 (p = 0.03), and −0.16 (p = 0.59). For high, medium, and low thiocyanate tertiles they were −1.67 (p = 0.0009), −0.68 (p = 0.09), and −0.49 (p = 0.11). Clear interactions between perchlorate and smoking were not seen with TSH or with T4 in women with urinary iodine levels ≥ 100 μg/L or in men. Conclusions These results suggest that thiocyanate in tobacco smoke and perchlorate interact in affecting thyroid function, and this effect can take place at commonly occurring perchlorate exposures. Agents other than tobacco smoke might cause similar interactions, and further research on these agents could help identify people who are particularly susceptible to perchlorate. PMID:17805424

  4. RNA extraction from various recalcitrant plant tissues with a cethyltrimethylammonium bromide-containing buffer followed by an acid guanidium thiocyanate-phenol-chloroform treatment.

    PubMed

    Suzuki, Yuji; Mae, Tadahiko; Makino, Amane

    2008-07-01

    High-quality total RNA was extracted using a cethyltrimethylammonium bromide-containing buffer followed by an acid guanidium thiocyanate-phenol-chloroform treatment from recalcitrant plant tissues such as tree leaves (pine, Norway spruce, ginkgo, Japanese cedar, rose), flowers (rose, Lotus japonicus) and storage tissues (seeds of Lotus japonicus and rice, sweet potato tuber, banana fruit). This protocol greatly reduced the time required for RNA extraction.

  5. Am(III) and Eu(III) extraction by aliquat.336 and benzyl substituted quaternary ammonium salts from nitrate and thiocyanate solutions

    SciTech Connect

    Chiarizia, R.; Gatrone, R.C.; Horwitz, E.P.

    1995-07-01

    The extraction of Am(III) and Eu(III) from HNO{sub 3} - LiNO{sub 3} or from HCOOH-NH{sub 4}SCN solutions by different quaternary ammonium salts dissolved in o-xylene was investigated as function of the aqueous phase composition. As extractants, the nitrate or thiocyanate salts of Aliquat.336, tridodecylmethylammonium, benzyl-dimethyldodecylammonium, p-methoxybenzyldimethyldodecylammonium and p-trifluoromethylbenzyldimethyldodecylammonium were used. The extraction data obtained with the thiocyanate- formic acid aqueous solutions were quantitatively interpreted by a reaction scheme that takes into account the aqueous metal complexation and the competition of formic acid and metal species for the extractant reaction center. The effect of the benzyl group (whether substituted or not) on the metal and acid extraction by the different quaternary ammonium salts was interpreted on the basis of the inductive effect of the substituents. In the thiocyanate system, Aliquat.336 provided the highest Am/Eu separation factors. 24 refs., 10 figs., 2 tabs.

  6. Combined capillary electrophoresis and high performance liquid chromatography studies on the kinetics and mechanism of the hydrogen peroxide-thiocyanate reaction in a weakly alkaline solution.

    PubMed

    Hu, Ying; Song, Yanan; Horváth, Attila K; Cui, Yin; Ji, Chen; Zhao, Yuemin; Gao, Qingyu

    2014-03-01

    The hydrogen peroxide-thiocyanate reaction has been reinvestigated by means of capillary electrophoresis and high performance liquid chromatography under weakly alkaline conditions at 25.0±0.1 °C. Concentration-time series of thiocyanate, sulfate and cyanate have been followed by capillary electrophoresis as well as that of thiocyanate and hydrogen peroxide by HPLC. It has been clearly demonstrated that OxSCN(-) (where x=1, 2 and 3) cannot be accumulated in detectable amount in contrast to the results of Christy and Egeberg, hence these species can only be regarded as short-lived intermediates. It has been shown that the overall rate law is first-order with respect to both reactants, but no pH-dependence was observed within the pH range of 8.86-10.08. A simple kinetic model has been proposed to fit all the concentration-time curves simultaneously at five different pHs demonstrating the powerful combination of the experimental techniques CE and HPLC with simultaneous evaluation of kinetic curves. It is also enlightened that the quality of the buffer strongly affects the rate of the overall reaction that increases in the order of application of ammonia, phosphate, carbonate and borate, respectively at a constant ionic strength and pH.

  7. Nickel(II) and copper(II) coordination polymers with 1,2-bis(tetrazol-1-yl)ethane and thiocyanate: Structure, supramolecular isomerism and magnetism

    NASA Astrophysics Data System (ADS)

    Liu, Pei-Pei; Wang, Yan-Qin; Tian, Chun-Yan; Peng, Hui-Qi; Gao, En-Qing

    2009-02-01

    Two heteroleptic coordination polymers with the flexible 1,2-bis(tetrazol-1-yl)ethane (btze) ligand, [Ni(btze) 2(SCN) 2] n ( 1) and [Cu(btze)(SCN) 2] n ( 2), have been synthesized in presence of thiocyanate. Compound 1 is composed of 1D chains with double btze bridges in the V-shaped gauche conformation, while 2 exhibits 2D coordination networks in which 1D chains with double N, S-thiocyanate bridges are cross-linked by btze bridges in the Z-shaped transoid conformation. In both compounds, the coordination motifs are stacked into 3D architectures through S···S and C-H···N interactions. The structures of 1 and a previously reported compound illustrate an interesting type of supramolecular isomerism. The two isomers exhibit almost identical 1D coordination structure and 2D hydrogen bonded superstructure, and the difference lies only in the interlayer packing associated with S···S contacts. Compound 2 exhibits weak antiferromagnetic interactions with J = 0.29 cm -1, consistent with the structural observation that the thiocyanate bridge adopts an equatorial-axial disposition between Cu(II) ions.

  8. Novel bimetallic thiocyanate-bridged Cu(II)-Hg(II) compounds-synthesis, X-Ray studies and magnetic properties

    SciTech Connect

    Machura, B.; Switlicka, A.; Zwolinski, P.; Mrozinski, J.; Kalinska, B.; Kruszynski, R.

    2013-01-15

    Seven novel heterobimetallic Cu/Hg polymers based on thiocyanate bridges have been synthesised and characterised by means of IR, EPR, magnetic measurements and single crystal X-Ray. Three of them, [Cu(pzH){sub 4}Hg(SCN){sub 4}]{sub n} (1) [Cu(indH){sub 4}Hg(SCN){sub 4}]{sub n} (2) and [Cu(ampy){sub 2}Hg(SCN){sub 4}]{sub n} (3), have one-dimensional coordination structure. Two compounds [Cu(pzH){sub 2}Hg(SCN){sub 4}]{sub n} (4) and [Cu(abzimH)Hg(SCN){sub 4}]{sub n} (5) form two-dimensional nets, whereas the complexes [Cu(pyCN){sub 2}Hg(SCN){sub 4}]{sub n} (6) and [Cu(pyCH(OH)(OMe)){sub 2}Hg(SCN){sub 4}]{sub n} (7) are three-dimensional coordination polymers. The chains of 1 are connected by the intermolecular N-H Bullet Bullet Bullet N hydrogen bonds to the three dimensional net. In 2 the N-H Bullet Bullet Bullet S hydrogen bonds link the polymeric chains to the two dimensional layer extending along crystallographic (0 0 1) plane. The polymeric chains of compound 3 are joined by the intermolecular N-H Bullet Bullet Bullet N and N-H Bullet Bullet Bullet S hydrogen bonds to the three dimensional net. The polymeric layers of 4 are connected by the intermolecular N-H Bullet Bullet Bullet N hydrogen bonds to the three dimensional net. - Graphical abstract: Novel bimetallic thiocyanate-bridged Cu(II)-Hg(II) compound-synthesis,X-Ray studies and magnetic properties. Highlights: Black-Right-Pointing-Pointer Novel heterobimetallic Cu/Hg coordination polymers were synthesised. Black-Right-Pointing-Pointer The multidimensional structures have been proved by single X-ray analysIs. Black-Right-Pointing-Pointer A variation in the crystalline architectures was observed depending on auxiliary ligands. Black-Right-Pointing-Pointer Magnetic measurements indicate weak exchange interaction between Cu(II) in the crystal lattices below 10 K.

  9. Spectrophotometric determination of trazodone, amineptine and amitriptyline hydrochlorides through ion-pair formation with molybdenum and thiocyanate

    NASA Astrophysics Data System (ADS)

    Mohamed, Gehad G.; Nour El-Dien, F. A.; Khalil, S. M.; Mohamed, Nehad A.

    2006-12-01

    Extraction spectrophotometric method has been developed for the determination of tricyclic drugs such as trazodone (TZH), amineptine (APH) and amitriptyline (ATPH) hydrochlorides in pure form and in the dosage forms coming from different Egyptian markets. The method based on the formation of ion-pairs between these drugs under investigation and inorganic complex of Mo(V)-thiocyanate followed by its extraction with methylene chloride. The optimum conditions for the ion-pairs formation are established. The method permits the determination of TZH, APH and ATPH over the concentration range of 2-28, 2-32 and 1-30 μg ml -1, respectively. The Sandell sensitivity ( S) is found to be 0.105, 0.138 and 0.118 g cm -2 for TZH, APH and ATPH, respectively. The SD is found to be 0.16-0.377, 0.12-0.259 and 0.091-0.286 and the R.S.D. are 0.14-0.55, 0.12-0.399 and 0.095-0.485 for TZH, APH and ATPH, respectively. The method is applicable for the assay of the investigated drugs in different dosage forms and the results are in good agreement with those obtained by the official method.

  10. Thiocyanate-free asymmetric ruthenium(II) dye sensitizers containing azole chromophores with near-IR light-harvesting capacity

    NASA Astrophysics Data System (ADS)

    Wu, Guohua; Kaneko, Ryuji; Islam, Ashraful; Zhang, Yaohong; Sugawa, Kosuke; Han, Liyuan; Shen, Qing; Bedja, Idriss; Gupta, Ravindra Kumar; Otsuki, Joe

    2016-11-01

    A new series of thiocyanate-free bis-tridentate Ru(II) complexes containing azole ligands as well as an organometallic Ru-C bond are synthesized, characterized, and evaluated in dye-sensitized solar cells (DSSCs). CF3-substituted pyrazolyl, CF3-substituted triazolyl, and tetrazolyl derivatives are employed as ligands in the three neutral complexes PYZ, TRZ, and TEZ dyes, respectively. Despite their different structures, all the three complexes exhibit similar absorption features and panchromatic absorption covering the visible and near-IR regions. By switching from a pyrazolyl via triazolyl to tetrazolyl moiety in the ligand, the photocurrent value, open-circuit voltage, and overall efficiency are increased accordingly under the same conditions. Among them, photon-to-current conversion efficiency (ƞ) of TEZ dye reaches the maximum of 6.44% with a short-circuit photocurrent density (Jsc) of 17.8 mA cm-2, an open-circuit photovoltage (Voc) of 0.54 V and fill factor (FF) of 0.67 under illumination of an AM1.5G solar simulator. TEZ dye shows a good long term light soaking stability and maintains up to more than 90% of the initial power conversion efficiency after 1000 h.

  11. Spectrophotometric determination of ampicillin, dicluxacillin, flucloxacillin and amoxicillin antibiotic drugs: ion-pair formation with molybdenum and thiocyanate.

    PubMed

    Mohamed, G G

    2001-02-01

    A sensitive spectrophotometric method is developed for the determination of some antibiotic drugs such as ampicillin (amp), dicluxacillin (dicl), flucloxacillin (fluc) and amoxicillin (amox). The method involves the formation of ion-pairs between these drugs under investigation and inorganic complex of Mo (V) thiocyanate followed by its extraction with methylene chloride. The optimum conditions for the ion-pairs formation are established. The method permits the determination of amp, dicl, fluc and amox over a concentration range of 1.5-77.5, 3-75, 1.5-79 and 7.5-75 microg ml(-1) respectively. The sensitivity (S) is found to be 0.017, 0.061, 0.014 and 0.073 microg cm(-2) for amp, dicl, fluc and amox, respectively. The method is simple, rapid, reproducible and accurate within +/- 1%. The method is applicable for the assay of the four drugs under investigation in different dosage forms and the results are in good agreement with those obtained by the official method.

  12. Novel bimetallic thiocyanate-bridged Cu(II)-Hg(II) compounds—synthesis, X-Ray studies and magnetic properties

    NASA Astrophysics Data System (ADS)

    Machura, B.; Świtlicka, A.; Zwoliński, P.; Mroziński, J.; Kalińska, B.; Kruszynski, R.

    2013-01-01

    Seven novel heterobimetallic Cu/Hg polymers based on thiocyanate bridges have been synthesised and characterised by means of IR, EPR, magnetic measurements and single crystal X-Ray. Three of them, [Cu(pzH)4Hg(SCN)4]n (1) [Cu(indH)4Hg(SCN)4]n (2) and [Cu(ampy)2Hg(SCN)4]n (3), have one-dimensional coordination structure. Two compounds [Cu(pzH)2Hg(SCN)4]n (4) and [Cu(abzimH)Hg(SCN)4]n (5) form two-dimensional nets, whereas the complexes [Cu(pyCN)2Hg(SCN)4]n (6) and [Cu(pyCH(OH)(OMe))2Hg(SCN)4]n (7) are three-dimensional coordination polymers. The chains of 1 are connected by the intermolecular N-H•••N hydrogen bonds to the three dimensional net. In 2 the N-H•••S hydrogen bonds link the polymeric chains to the two dimensional layer extending along crystallographic (0 0 1) plane. The polymeric chains of compound 3 are joined by the intermolecular N-H•••N and N-H•••S hydrogen bonds to the three dimensional net. The polymeric layers of 4 are connected by the intermolecular N-H•••N hydrogen bonds to the three dimensional net.

  13. Urea as a long-term stable alternative to guanidium thiocyanate additive in dye-sensitized solar cell

    NASA Astrophysics Data System (ADS)

    Kim, Mi-Jeong; Park, Nam-Gyu

    2012-09-01

    Photovoltaic performance of 0.05 M urea-contained redox electrolyte is compared to that of 0.05 M guanidinium thiocyanate (GSCN)-contained one in dye-sensitized solar cell. No significant difference in the initial photovoltaic performance is observed, which means that the role of urea additive is similar to that of GSCN. Initial solar-to-electrical conversion efficiency of the device containing GSCN shows 7% that is diminished to 5.8% after 40 days, whereas the device containing urea exhibits stable photovoltaic performance showing that initial efficiency of 7.2% is almost remained unchanged after 40 days (7.1%). The lowered efficiency of the GSCN-contained device is mainly due to the decreased photocurrent density, which is ascribed to the formation of needle-shaped crystals on TiO2 layer. Infrared spectroscopic study confirms that the crystals are dye analogue, which is indicative of dye desorption in the presence of GSCN. On the other hand, no crystals are formed in the urea-contained electrolyte, which implies that dye desorption is negligible. Urea additive is thus found to be less reactive in dye desorption than GSCN, leading to long-term stability.

  14. The effect of 1:2 Ag(I) thiocyanate complexes in MCF-7 breast cancer cells.

    PubMed

    Ferreira, Eloise; Munyaneza, Appollinaire; Omondi, Bernard; Meijboom, Reinout; Cronjé, Marianne J

    2015-08-01

    There is much interest currently in the design of metal compounds as drugs and various metal compounds are already in clinical use. These include gold(I) compounds such as auranofin and the anti-cancer platinum(II) complex, cisplatin. Bis-chelated gold(I) phosphine complexes have also shown great potential as anticancer agents, however, their efficacy has been limited by their high toxicity. In this study, silver(I) thiocyanate compounds linked to four specific ligands, were synthesized and characterized. These silver-phosphine adducts included [AgSCN{P(4-MeC6H4)3}2]2 (1); [AgSCN{P(4-ClC6H4)3}2]2 (2); [AgSCN{P(4-MeOC6H4)3}2]2 (3); [AgSCN(PPh3)2]2 (4). The compounds were found to be toxic to MCF-7 breast cancer cells while the ligands on their own were not toxic. Our findings further indicate that the silver(I) phosphine compounds induce apoptotic cell death in these breast cancer cells. In addition, the compounds were not toxic to nonmalignant fibroblast cells at the IC50 concentrations. This is an indication that the compounds show selectivity towards the cancer cells. PMID:26049979

  15. Resonant Rayleigh scattering for the determination of trace amounts of mercury (II) with thiocyanate and basic triphenylmethane dyes

    SciTech Connect

    Liu, S.; Liu, Z.; Zhou, G.

    1998-05-01

    Intense resonance Rayleigh scattering (RRS) appears when mercury (II) reacts with thiocyanate and a basic triphenylmethane dye (BTPMD), such as crystal violet (CV), ethyl violet (EV), brilliant green (BG), malachite green (MG) or indine green (IG), to form an ion-association complex of the type (BTPMD){sub 2}[Hg(SCN){sub 4}]. The characteristics of RRS spectra of the ion-association complexes and suitable conditions for the reactions were investigated. The intensity of RRS is directly proportional to the concentration of mercury (II) in the range of 0--2.0 {micro}g/25 ml. The RRS methods have very high sensitivities for determination of mercury (II); their detection limits are between 1.68 ng/ml and 6.00 ng/ml on different dye systems. The effects of foreign ions and ways to improve the selectivity were studied. The new highly sensitive methods for the determination of trace amounts of mercury based on the RRS of the ion-association complexes have been developed.

  16. Colorimetric and atomic absorption spectrometric determination of mucolytic drug ambroxol through ion-pair formation with iron and thiocyanate.

    PubMed

    Levent, Abdulkadir; Sentürk, Zühre

    2010-09-01

    Colorimetric and atomic absorption spectrometric methods have been developed for the determination of mucolytic drug Ambroxol. These procedures depend upon the reaction of iron(III) metal ion with the drug in the presence of thiocyanate ion to form stable ion-pair complex which extractable chloroform. The red-coloured complex was determined either colorimetrically at 510 nm or by indirect atomic absorption spectrometry (AAS) via the determination of the iron content in the formed complex. The optimum experimental conditions for pH, concentrations of Fe(3+) and SCN(-), shaking time, phase ratio, and the number of extractions were determined. Under the proposed conditions, linearity was obeyed in the concentration ranges 4.1x10(-6) - 5.7x10(-5) M (1.7-23.6 µg mL(-1)) using both methods, with detection limits of 4.6x10(-7) M (0.19 µg mL(-1)) for colorimetry and 1.1x10(-6) M (0.46 µg mL(-1)) for AAS. The proposed methods were applied for the determination of Ambroxol in tablet dosage forms. The results obtained were statistically analyzed and compared with those obtained by applying the high-performance liquid chromatographic method with diode-array detection.

  17. The crystal structure of the thiocyanate-forming protein from Thlaspi arvense, a kelch protein involved in glucosinolate breakdown.

    PubMed

    Gumz, Frauke; Krausze, Joern; Eisenschmidt, Daniela; Backenköhler, Anita; Barleben, Leif; Brandt, Wolfgang; Wittstock, Ute

    2015-09-01

    Kelch repeat-containing proteins are involved in diverse cellular processes, but only a small subset of plant kelch proteins has been functionally characterized. Thiocyanate-forming protein (TFP) from field-penny cress, Thlaspi arvense (Brassicaceae), is a representative of specifier proteins, a group of kelch proteins involved in plant specialized metabolism. As components of the glucosinolate-myrosinase system of the Brassicaceae, specifier proteins determine the profile of bioactive products formed when plant tissue is disrupted and glucosinolates are hydrolyzed by myrosinases. Here, we describe the crystal structure of TaTFP at a resolution of 1.4 Å. TaTFP crystallized as homodimer. Each monomer forms a six-blade β-propeller with a wide "top" and a narrower "bottom" opening with distinct strand-connecting loops protruding far beyond the lower propeller surface. Molecular modeling and mutational analysis identified residues for glucosinolate aglucone and Fe(2+) cofactor binding within these loops. As the first experimentally determined structure of a plant kelch protein, the crystal structure of TaTFP not only enables more detailed mechanistic studies on glucosinolate breakdown product formation, but also provides a new basis for research on the diverse roles and mechanisms of other kelch proteins in plants. PMID:26260516

  18. Determination of heavy metals at sub-ppm levels in seawater and dialysis solutions by FAAS after tetrakis(pyridine)-nickel(II)bis(thiocyanate) coprecipitation.

    PubMed

    Sahin, Uğur; Kartal, Senol; Ulgen, Ahmet

    2008-06-01

    A coprecipitation method has been developed for the determination of Cr(III), Mn(II), Fe(III), Co(II), Cu(II), Cd(II) and Pb(II) ions in aqueous samples by flame atomic absorption spectrometry (FAAS) with the combination of pyridine, nickel(II) as a carrier element and potassium thiocyanate as an auxiliary complexing agent. The obtained coprecipitates were dissolved with nitric acid and measured by FAAS. The coprecipitation conditions, such as the effect of the pH, amounts of nickel, pyridine and potassium thiocyanate, sample volume, and the standing time of the precipitate formation were examined in detail. It was found that the metal ions studied were quantitatively coprecipitated with tetrakis(pyridine)-nickel(II)bis(thiocyanate) precipitate (TP-Ni-BT) in the pH range of 9.0 - 10.5. The reliability of the results was evaluated by recovery tests, using synthetic seawater solutions spiked with the analyte metal ions. The obtained recoveries ranged from 96 to 101% for all of the metal ions investigated. The proposed method was validated by analyses of two certified reference materials (NIST SRM 2711 Montana soil and HPS Certified Waste Water Trace Metals Lot #D532205). It was also successfully applied to seawater and dialysis solution samples. The detection limits (n = 25, 3s) were in the range of 0.01-2.44 microg l(-1) for the studied elements and the relative standard deviations were < or =6%, which indicated that this method could fully satisfy the requirements for analysis of such samples as seawater and dialysis solution having high salt contents. PMID:18544864

  19. Role of electrostatics in differential binding of RalGDS to Rap mutations E30D and K31E investigated by vibrational spectroscopy of thiocyanate probes.

    PubMed

    Ragain, Christina M; Newberry, Robert W; Ritchie, Andrew W; Webb, Lauren J

    2012-08-01

    The human protein Rap1A (Rap) is a member of the Ras superfamily of GTPases that binds to the downstream effector Ral guanine nucleotide dissociation stimulator (RalGDS). Although Ras and Rap have nearly identical amino acid sequences and structures along the effector binding surface, the charge reversal mutation Rap K31E has previously been shown to increase the dissociation constant of Rap-RalGDS docking to values similar to that of Ras-RalGDS docking. This indicates that the difference in charge at position 31 could provide a mechanism for Ral to distinguish two structurally similar but functionally distinct GTPases, which would be of vital importance for appropriate biological function. In this report, vibrational Stark effect spectroscopy, dissociation constant measurements, and molecular dynamics simulations were used to investigate the role that electrostatic field differences caused by the charge reversal mutation Rap K31E play in determining the binding specificity of RalGDS to Rap versus Ras. To do this, six variants of RalGDS carrying a thiocyanate electrostatic probe were docked with three Rap mutants, E30D, K31E, and E30D/K31E. The change in absorption energy of the thiocyanate probe caused by RalGDS docking to these Rap variants was then compared to that observed with wild-type Ras. Three trends emerged: the expected reversion behavior, an additive behavior of the two single mutations, and cancelation of the effects of each single mutation in the double mutant. These observations are explained with a physical model of the position of the thiocyanate probe with respect to the mutated residue based on molecular dynamics simulations.

  20. New family of thiocyanate-bridged Re(IV)-SCN-M(II) (M = Ni, Co, Fe, and Mn) heterobimetallic compounds: synthesis, crystal structure, and magnetic properties.

    PubMed

    González, Ricardo; Acosta, Alvaro; Chiozzone, Raúl; Kremer, Carlos; Armentano, Donatella; De Munno, Giovanni; Julve, Miguel; Lloret, Francesc; Faus, Juan

    2012-05-21

    The heterobimetallic complexes of formula [(Me(2)phen)(2)M(μ-NCS)Re(NCS)(5)]·CH(3)CN [Me(2)phen = 2,9-dimethyl-1,10-phenanthroline and M = Ni (1), Co (2), Fe (3), and Mn (4)] have been prepared, and their crystal structures have been determined by X-ray diffraction on single crystals. Compounds 1-4 crystallize in the monoclinic C2/c space group, and their structure consists of neutral [(Me(2)phen)(2)M(μ-NCS)Re(NCS)(5)] heterodinuclear units with a Re-SCN-M bridge. Each Re(IV) ion in this series is six-coordinated with one sulfur and five nitrogen atoms from six thiocyanate groups building a somewhat distorted octahedral environment, whereas the M(II) metal ions are five-coordinated with four nitrogen atoms from two bidentate Me(2)phen molecules and a nitrogen atom from the bridging thiocyanate describing distorted trigonal bipyramidal surroundings. The values of the Re···M separation through the thiocyanate bridge in 1-4 vary in the range 5.903(1)-6.117(3) Å. The magnetic properties of 1-4 as well as those of the parent mononuclear Re(IV) compounds (NBu(4))(2)[Re(NCS)(6)] (A1) (NBu(4)(+) = tetra-n-butylammonium cation) and [Zn(NO(3))(Me(2)phen)(2)](2)[Re(NCS)(5)(SCN)] (A2) were investigated in the temperature range 1.9-300 K. Weak antiferromagnetic interactions between the Re(IV) and M(II) ions across the bridging thiocyanate were found in 1-4 [J = -4.3 (1), -2.4 (2), -1.8 (3), and -1.2 cm(-1) (4), the Hamiltonian being defined as Ĥ = -JŜ(Re)·Ŝ(M)]. The magnetic behavior of A2 is that of a magnetically diluted Re(IV) complex with a large and positive value of the zero-field splitting for the ground level (D(Re) = +37.0 cm(-1)). In the case of A1, although its magnetic behavior is similar to that of A2 in the high-temperature range (D(Re) being +19.0 cm(-1)), it exhibits a weak ferromagnetism below 3.0 K with a canting angle of 1.3°.

  1. The effects of perchlorate, nitrate, and thiocyanate on free thyroxine for potentially sensitive subpopulations of the 2001-2002 and 2007-2008 National Health and Nutrition Examination Surveys.

    PubMed

    Suh, Mina; Abraham, Liz; Hixon, J Gregory; Proctor, Deborah M

    2014-11-01

    Among women with urinary iodine concentration <100 μg/l in the 2001-2002 National Health and Nutrition Examination Survey (NHANES), urinary perchlorate was associated with significant changes in thyroid stimulating hormone and total thyroxine (T4). Although perchlorate, nitrate, and thiocyanate all potentially act to inhibit iodide uptake, free T4 was not found to be associated with exposure to these chemicals in the same data. Fetuses of pregnant mothers with iodine deficiency are thought to be a sensitive subpopulation for perchlorate exposure, but the potential associations between free T4 and exposure to these chemicals among pregnant mothers in NHANES 2001-2002 and 2007-2008 have not been specifically evaluated to date. This study investigates the potential associations between urinary perchlorate, nitrate, and thiocyanate and serum free T4 in individuals with low urinary iodine levels and pregnant women. Multivariate regression models of free T4 were conducted and included urinary perchlorate, nitrate, thiocyanate, and covariates known to have an impact on the thyroid (anti-thyroid peroxidase (TPO) antibodies, age, race/ethnicity, body mass index, and hours of fasting). Meta-analyses were also conducted on non-pregnant and on pregnant women from the two survey cycles. Urinary nitrate was associated with serum free T4 in non-pregnant women of NHANES 2001-2002 who had urinary iodine ≥100 μg/l. In the meta-analysis, urinary perchlorate, nitrate, and thiocyanate were significant predictors of serum free T4 in non-pregnant women. No association was found in men and pregnant women. TPO antibodies were significant predictors of free T4 among non-pregnant women only when the models included urinary perchlorate, nitrate, or thiocyanate. Risk assessment for perchlorate exposure should consider co-exposure to nitrate and thiocyanate.

  2. Ultrafast vibrational spectroscopy (2D-IR) of CO{sub 2} in ionic liquids: Carbon capture from carbon dioxide’s point of view

    SciTech Connect

    Brinzer, Thomas; Berquist, Eric J.; Ren, Zhe; Dutta, Samrat; Johnson, Clinton A.; Krisher, Cullen S.; Lambrecht, Daniel S.; Garrett-Roe, Sean

    2015-06-07

    The CO{sub 2}ν{sub 3} asymmetric stretching mode is established as a vibrational chromophore for ultrafast two-dimensional infrared (2D-IR) spectroscopic studies of local structure and dynamics in ionic liquids, which are of interest for carbon capture applications. CO{sub 2} is dissolved in a series of 1-butyl-3-methylimidazolium-based ionic liquids ([C{sub 4}C{sub 1}im][X], where [X]{sup −} is the anion from the series hexafluorophosphate (PF{sub 6}{sup −}), tetrafluoroborate (BF{sub 4}{sup −}), bis-(trifluoromethyl)sulfonylimide (Tf{sub 2}N{sup −}), triflate (TfO{sup −}), trifluoroacetate (TFA{sup −}), dicyanamide (DCA{sup −}), and thiocyanate (SCN{sup −})). In the ionic liquids studied, the ν{sub 3} center frequency is sensitive to the local solvation environment and reports on the timescales for local structural relaxation. Density functional theory calculations predict charge transfer from the anion to the CO{sub 2} and from CO{sub 2} to the cation. The charge transfer drives geometrical distortion of CO{sub 2}, which in turn changes the ν{sub 3} frequency. The observed structural relaxation timescales vary by up to an order of magnitude between ionic liquids. Shoulders in the 2D-IR spectra arise from anharmonic coupling of the ν{sub 2} and ν{sub 3} normal modes of CO{sub 2}. Thermal fluctuations in the ν{sub 2} population stochastically modulate the ν{sub 3} frequency and generate dynamic cross-peaks. These timescales are attributed to the breakup of ion cages that create a well-defined local environment for CO{sub 2}. The results suggest that the picosecond dynamics of CO{sub 2} are gated by local diffusion of anions and cations.

  3. Ultrafast vibrational spectroscopy (2D-IR) of CO2 in ionic liquids: Carbon capture from carbon dioxide's point of view

    NASA Astrophysics Data System (ADS)

    Brinzer, Thomas; Berquist, Eric J.; Ren, Zhe; Dutta, Samrat; Johnson, Clinton A.; Krisher, Cullen S.; Lambrecht, Daniel S.; Garrett-Roe, Sean

    2015-06-01

    The CO2ν3 asymmetric stretching mode is established as a vibrational chromophore for ultrafast two-dimensional infrared (2D-IR) spectroscopic studies of local structure and dynamics in ionic liquids, which are of interest for carbon capture applications. CO2 is dissolved in a series of 1-butyl-3-methylimidazolium-based ionic liquids ([C4C1im][X], where [X]- is the anion from the series hexafluorophosphate (PF 6- ), tetrafluoroborate (BF 4- ), bis-(trifluoromethyl)sulfonylimide (Tf2N-), triflate (TfO-), trifluoroacetate (TFA-), dicyanamide (DCA-), and thiocyanate (SCN-)). In the ionic liquids studied, the ν3 center frequency is sensitive to the local solvation environment and reports on the timescales for local structural relaxation. Density functional theory calculations predict charge transfer from the anion to the CO2 and from CO2 to the cation. The charge transfer drives geometrical distortion of CO2, which in turn changes the ν3 frequency. The observed structural relaxation timescales vary by up to an order of magnitude between ionic liquids. Shoulders in the 2D-IR spectra arise from anharmonic coupling of the ν2 and ν3 normal modes of CO2. Thermal fluctuations in the ν2 population stochastically modulate the ν3 frequency and generate dynamic cross-peaks. These timescales are attributed to the breakup of ion cages that create a well-defined local environment for CO2. The results suggest that the picosecond dynamics of CO2 are gated by local diffusion of anions and cations.

  4. Spectrophotometric determination of some anti-tussive and anti-spasmodic drugs through ion-pair complex formation with thiocyanate and cobalt(II) or molybdenum(V)

    NASA Astrophysics Data System (ADS)

    El-Shiekh, Ragaa; Zahran, Faten; El-Fetouh Gouda, Ayman Abou

    2007-04-01

    Two rapid, simple and sensitive extractive specrophotometric methods has been developed for the determination of anti-tussive drugs, e.g., dextromethorphan hydrobromide (DEX) and pipazethate hydrochloride (PiCl) and anti-spasmodic drugs, e.g., drotaverine hydrochloride (DvCl) and trimebutine maleate (TM) in bulk and in their pharmaceutical formulations. The proposed methods depend upon the reaction of cobalt(II)-thiocyanate (method A) and molybdenum(V)-thiocyanate ions (method B) with the cited drugs to form stable ion-pair complexes which extractable with an n-butnol-dichloromethane solvent mixture (3.5:6.5) and methylene chloride for methods A and B, respectively. The blue and orange red color complexes are determined either colorimetrically at λmax 625 nm (using method A) and 467 or 470 nm for (DEX and PiCl) or (DvCl and TM), respectively (using method B). The concentration range is 20-400 and 2.5-50 μg mL -1 for methods A and B, respectively. The proposed method was successfully applied for the determination of the studied drugs in pure and in pharmaceutical formulations applying the standard additions technique and the results obtained in good agreement well with those obtained by the official method.

  5. Spectrophotometric determination of some anti-tussive and anti-spasmodic drugs through ion-pair complex formation with thiocyanate and cobalt(II) or molybdenum(V).

    PubMed

    El-Shiekh, Ragaa; Zahran, Faten; El-Fetouh Gouda, Ayman Abou

    2007-04-01

    Two rapid, simple and sensitive extractive specrophotometric methods has been developed for the determination of anti-tussive drugs, e.g., dextromethorphan hydrobromide (DEX) and pipazethate hydrochloride (PiCl) and anti-spasmodic drugs, e.g., drotaverine hydrochloride (DvCl) and trimebutine maleate (TM) in bulk and in their pharmaceutical formulations. The proposed methods depend upon the reaction of cobalt(II)-thiocyanate (method A) and molybdenum(V)-thiocyanate ions (method B) with the cited drugs to form stable ion-pair complexes which extractable with an n-butnol-dichloromethane solvent mixture (3.5:6.5) and methylene chloride for methods A and B, respectively. The blue and orange red color complexes are determined either colorimetrically at lambdamax 625 nm (using method A) and 467 or 470 nm for (DEX and PiCl) or (DvCl and TM), respectively (using method B). The concentration range is 20-400 and 2.5-50 microg mL-1 for methods A and B, respectively. The proposed method was successfully applied for the determination of the studied drugs in pure and in pharmaceutical formulations applying the standard additions technique and the results obtained in good agreement well with those obtained by the official method. PMID:17142094

  6. Instrumental methods of analysis of sulfur compounds in synfuel process streams. Quarterly technical progress report for April-June 1984. [Sulfidic, polysulfidic, thiosulfate, sulfite, sulfate, thiocyanate

    SciTech Connect

    Jordan, J.; Sexton, E.; Talbott, J.; Yakupkovic, J.

    1984-07-01

    Task 1: methods development for the speciation of the polysulfides. Work on this task has been completed in December 1983 and reported accordingly in DOE/PC/40783-T13. Task 2: methods development for the speciation of dithionite and polythionates. Electrochemical reduction of tetrathionate and pentathionate at the dropping mercury electrode (DME) proceeds through a mechanism involving specific adsorption of the reactant at the DME surface and yielding polarographic waves at -0.2 volt (versus the saturated calomel electrode) in aqueous solution. Ethanol interferes with the specific adsorption of tetrathionate and pentathionate in a range of potentials between 0.0 and -1.1 volt, because EtOH is preferentially adsorbed. This results in a shift of the polarographic half-wave potentials of tetrathionate and pentathionate, which facilitates their determination in polythionate mixtures. On the other hand, the polarographic reduction of trithionate is unaffected by ethanol, because it occurs at -1.5 volt where ethanol is not adsorbed at the surface of the DME. Task 3: total accounting of the sulfur balance in representative samples of synfuel process streams. Analyses of two aqueous gasifier effluents from Grand Forks, ND, were performed. An untreated specimen contained sulfidic and polysulfidic sulfur, thiosulfate and thiocyanate. On the other hand, sulfite, sulfate, and thiocyanate were the only sulfur moieties observed in the Grand Forks sample which had been stripped at PETC. 7 references, 1 figure, 3 tables.

  7. Acetylation of Starch with Vinyl Acetate in Imidazolium Ionic Liquids and Characterization of Acetate Distribution

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Starch was acetylated with vinyl acetate in different 1-butyl-3-methylimidazolium (BMIM) salts as solvent in effort to produce starches with different acetylation patterns. Overall degree of substitution was much higher for basic anions such as acetate and dicyanimide (dca) than for neutral anions ...

  8. Esterification of Starch in Ionic Liquids

    Technology Transfer Automated Retrieval System (TEKTRAN)

    We shall discuss the use of various ionic liquids in the preparation of starch esters. Starch was reacted with vinyl acetate in different 1-butyl-3-methylimidazolium (bmim) salts as solvents in an effort to produce starches with different acetylation patterns. Overall degree of substitution (DS) w...

  9. Ionic Liquid as a Solvent and Catalyst for Acylation of Maltodextrin

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  10. Ionic liquid catalysed reaction of thiols with α,β-unsaturated carbonyl compounds--remarkable influence of the C-2 hydrogen and the anion.

    PubMed

    Sarkar, Anirban; Roy, Sudipta Raha; Chakraborti, Asit K

    2011-04-21

    Hydrogen bond induced reactivity and selectivity control in the 1-butyl-3-methylimidazolium based ionic liquid catalysed reaction of thiols with α,β-unsaturated carbonyl compounds is reported with remarkable influence of the anion and the C-2 hydrogen in catalytic activity and reversal of selectivity.

  11. Ionic liquid-in-oil microemulsions.

    PubMed

    Eastoe, Julian; Gold, Sarah; Rogers, Sarah E; Paul, Alison; Welton, Tom; Heenan, Richard K; Grillo, Isabelle

    2005-05-25

    Phase stability and small-angle neutron scattering (SANS) data show that surfactant-stabilized nanodomains of a typical ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate [bmim][BF4]) may be dispersed by the nonionic surfactant Triton-X100 in cyclohexane. Analyses of these SANS data are consistent with the formation of ionic liquid-in-oil microemulsion droplets. PMID:15898765

  12. The single-step method of RNA isolation by acid guanidinium thiocyanate-phenol-chloroform extraction: twenty-something years on.

    PubMed

    Chomczynski, Piotr; Sacchi, Nicoletta

    2006-01-01

    Since its introduction, the 'single-step' method has become widely used for isolating total RNA from biological samples of different sources. The principle at the basis of the method is that RNA is separated from DNA after extraction with an acidic solution containing guanidinium thiocyanate, sodium acetate, phenol and chloroform, followed by centrifugation. Under acidic conditions, total RNA remains in the upper aqueous phase, while most of DNA and proteins remain either in the interphase or in the lower organic phase. Total RNA is then recovered by precipitation with isopropanol and can be used for several applications. The original protocol, enabling the isolation of RNA from cells and tissues in less than 4 hours, greatly advanced the analysis of gene expression in plant and animal models as well as in pathological samples, as demonstrated by the overwhelming number of citations the paper gained over 20 years. PMID:17406285

  13. Effects of thiocyanate on the formation of free cyanide during chlorination and ultraviolet disinfection of publicly owned treatment works secondary effluent.

    PubMed

    Zheng, Anping; Dzombak, David A; Luthy, Richard G

    2004-01-01

    Cyanide has been detected in effluent of some publicly owned treatment works (POTWs) at levels exceeding influent concentration. Thiocyanate (SCN-) is a cyanide-related compound encountered in most POTW influents and may be decomposed to free cyanide (CN-) under some circumstances. Effects of SCN- on the formation of cyanide during chlorination and UV disinfection were studied through a laboratory study with synthetic solutions and POTW secondary effluent. Results indicated that CN- was detected in SCN- solutions after chlorination in which the chlorine dose or reaction time was not sufficient to destroy SCN-completely, thus ensuring no residual chlorine to destroy any CN-produced. It was also found that SCN can be broken down to yield cyanide by UV irradiation. In addition, SCN- was observed to cause significant positive error in the conventional total cyanide analysis technique involving acidic distillation and colorimetric measurement when nitrate was present in the sample.

  14. Urinary heavy metals, phthalates, phenols, thiocyanate, parabens, pesticides, polyaromatic hydrocarbons but not arsenic or polyfluorinated compounds are associated with adult oral health: USA NHANES, 2011-2012.

    PubMed

    Shiue, Ivy

    2015-10-01

    Links between environmental chemicals and human health have emerged over the last few decades, but the effects on oral health have been less studied. Therefore, it was aimed to study the relationships of different sets of urinary chemical concentrations and adult oral health conditions in a national and population-based setting. Data was retrieved from the United States National Health and Nutrition Examination Surveys, 2011-2012 including demographics, self-reported oral health conditions and urinary environmental chemical concentrations (one third representative sample of the study population). Chi-square test, t test, and survey-weighted logistic and multi-nominal regression modeling were performed. Of 4566 American adults aged 30-80, 541 adults (11.9 %) reported poor teeth health while 1020 adults (22.4 %) reported fair teeth. Eight hundred fifty-five people (19.1 %) claimed to have gum disease, presented with higher levels of urinary cadmium, cobalt and polyaromatic hydrocarbons. Six hundred three adults (13.3 %) had bone loss around the mouth, presented with higher levels of cadmium, nitrate, thiocyanate, propyl paraben and polyaromatic hydrocarbons. Eight hundred forty-five adults (18.5 %) had tooth loose not due to injury, presented with higher level of cadmium, thiocyanate and polyaromatic hydrocarbons. Eight hundred forty-five adults (18.5 %) with higher levels of lead, uranium, polyaromatic hydrocarbons but lower level of triclosan noticed their teeth did not look right. Three hundred fifty-one adults (7.7 %) often had aching in the mouth and 650 (14.3 %) had it occasionally, presented with higher levels of phthalates, pesticides and polyaromatic hydrocarbons. Benzophenone-3 and triclosan elicited protective effects. Regulation of environmental chemicals in prevention of adult oral health might need to be considered in future health and environmental policies. PMID:26018285

  15. Urinary heavy metals, phthalates, phenols, thiocyanate, parabens, pesticides, polyaromatic hydrocarbons but not arsenic or polyfluorinated compounds are associated with adult oral health: USA NHANES, 2011-2012.

    PubMed

    Shiue, Ivy

    2015-10-01

    Links between environmental chemicals and human health have emerged over the last few decades, but the effects on oral health have been less studied. Therefore, it was aimed to study the relationships of different sets of urinary chemical concentrations and adult oral health conditions in a national and population-based setting. Data was retrieved from the United States National Health and Nutrition Examination Surveys, 2011-2012 including demographics, self-reported oral health conditions and urinary environmental chemical concentrations (one third representative sample of the study population). Chi-square test, t test, and survey-weighted logistic and multi-nominal regression modeling were performed. Of 4566 American adults aged 30-80, 541 adults (11.9 %) reported poor teeth health while 1020 adults (22.4 %) reported fair teeth. Eight hundred fifty-five people (19.1 %) claimed to have gum disease, presented with higher levels of urinary cadmium, cobalt and polyaromatic hydrocarbons. Six hundred three adults (13.3 %) had bone loss around the mouth, presented with higher levels of cadmium, nitrate, thiocyanate, propyl paraben and polyaromatic hydrocarbons. Eight hundred forty-five adults (18.5 %) had tooth loose not due to injury, presented with higher level of cadmium, thiocyanate and polyaromatic hydrocarbons. Eight hundred forty-five adults (18.5 %) with higher levels of lead, uranium, polyaromatic hydrocarbons but lower level of triclosan noticed their teeth did not look right. Three hundred fifty-one adults (7.7 %) often had aching in the mouth and 650 (14.3 %) had it occasionally, presented with higher levels of phthalates, pesticides and polyaromatic hydrocarbons. Benzophenone-3 and triclosan elicited protective effects. Regulation of environmental chemicals in prevention of adult oral health might need to be considered in future health and environmental policies.

  16. 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. PMID:27142029

  17. 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.

  18. Colorimetric Determination of the Iron(III)-Thiocyanate Reaction Equilibrium Constant with Calibration and Equilibrium Solutions Prepared in a Cuvette by Sequential Additions of One Reagent to the Other

    ERIC Educational Resources Information Center

    Nyasulu, Frazier; Barlag, Rebecca

    2011-01-01

    The well-known colorimetric determination of the equilibrium constant of the iron(III-thiocyanate complex is simplified by preparing solutions in a cuvette. For the calibration plot, 0.10 mL increments of 0.00100 M KSCN are added to 4.00 mL of 0.200 M Fe(NO[subscript 3])[subscript 3], and for the equilibrium solutions, 0.50 mL increments of…

  19. Use of magnetic beads versus guanidium thiocyanate-phenol-chloroform RNA extraction followed by polymerase chain reaction for the rapid, sensitive detection of enterovirus RNA.

    PubMed

    Beaulieux, F; See, D M; Leparc-Goffart, I; Aymard, M; Lina, B

    1997-01-01

    The current study compares the sensitivity of RNA extraction using magnetic beads versus that of a standard extraction method. Streptavadin-coated magnetic beads were labelled with a biotinylated, enterovirus-specific oligonucleotide. RNA was extracted using labelled beads or guanidium thiocyanate-phenol-chloroform from 1, 0.1 and 0.01 TCID50/100 microliters of stock coxsackievirus types A9 and B3, echovirus type 11, enterovirus type 70 and poliovirus type 1. Each strain was tested three times. RNA extraction using magnetic beads was > 50% faster than the standard method. The RNA was amplified using RT-PCR, and the products were detected using agarose gel electrophoresis; 6/15 and 7/15 samples at an initial concentration of 0.01 TCID50/100 microliters were detected using magnetic beads or standard extraction, respectively. Negative-stain electron microscopy was used to determine that 0.01 TCID50/100 microliters of coxsackievirus B3 contained approximately 3 genomes. Thus, use of magnetic beads labelled with an enterovirus-specific oligonucleotide was less toxic, more rapid and as sensitive as the current standard RNA extraction method.

  20. Molecular structure of mercury(II) thiocyanate complexes based on DFT calculations and experimental UV-electron spectroscopy and Raman studies

    NASA Astrophysics Data System (ADS)

    Elijošiutė, Erika; Eicher-Lorka, Olegas; Griškonis, Egidijus; Matulaitienė, Ieva; Jankūnaitė, Dalia; Denafas, Gintaras

    2013-11-01

    In this work, we report a combined experimental and theoretical study on molecular structure, vibrational and electronic spectra of [Hg(SCN)n]2-n complexes (where n = 2, 3, 4) in the aqueous solution. Molecular modeling of the mercury(II) complexes were done by the density functional theory (DFT) method using B3LYP functional with Stuttgart relativistic ECP 78MWB basis set for Hg and 6-311++G(d,p) basis set for all other atoms. The effect of different solvation models with explicit (ligand) and/or implicit water environment upon its geometry, vibrational frequencies and UV spectrum have been studied. The influence of H2O/D2O exchange on the experimental and calculated vibrational frequencies of studied complexes has been established. The double-peak character of the νHgsbnd S vibrational mode of the all analyzed mercury complexes and νCtbnd N mode of [Hg(SCN)3H2O]- complex, respectively, were proposed here for the first time. The formation of four-coordinated Hg(II) complexes with thiocyanate and (or) water ligands was verified.

  1. A dual-mode colorimetric and fluorometric "light on" sensor for thiocyanate based on fluorescent carbon dots and unmodified gold nanoparticles.

    PubMed

    Zhao, Dan; Chen, Chuanxia; Lu, Lixia; Yang, Fan; Yang, Xiurong

    2015-12-21

    A novel, highly sensitive and selective dual-readout (colorimetric and fluorometric) sensor based on fluorescent carbon dots (CDs) and unmodified gold nanoparticles (AuNPs) for the detection of thiocyanate (SCN(-)) was proposed. Amino-functionalized CDs could be readily adsorbed onto the surface of citrate-stabilized AuNPs through Au-N interactions, leading to the aggregation of AuNPs and the nonfluorescent off-state of CDs arising from potential fluorescence resonance energy transfer (FRET). However, SCN(-) had a stronger affinity toward AuNPs and could compete with CDs to bind onto the surface of AuNPs in priority, which prevented the aggregation of AuNPs and fluorescence quenching of CDs. Correspondingly, both the colorimetric and fluorometric signals remained "light-on". The color of the sensing solution remained red and the fluorescence remained unquenched. A distinguishable change in the color was observed at a SCN(-) concentration of 1 μM by the naked eye and a detection limit as low as 0.036 μM was obtained by virtue of fluorescence spectroscopy. Both colorimetric and fluorometric sensors exhibited excellent selectivity toward SCN(-) over other common metallic ions and anions. In addition, such a sensing assay featured simplicity, rapidity, cost-effectiveness and ease of operation without further modification. The accuracy and precision were evaluated based on the quantitative detection of SCN(-) in tap water and saliva samples with satisfactory results. PMID:26567774

  2. Glass transition dynamics and conductivity scaling in ionic deep eutectic solvents: The case of (acetamide + lithium nitrate/sodium thiocyanate) melts

    NASA Astrophysics Data System (ADS)

    Tripathy, Satya N.; Wojnarowska, Zaneta; Knapik, Justyna; Shirota, Hideaki; Biswas, Ranjit; Paluch, Marian

    2015-05-01

    A detailed investigation on the molecular dynamics of ionic deep eutectic solvents (acetamide + lithium nitrate/sodium thiocyanate) is reported. The study was carried out employing dielectric relaxation spectroscopy covering seven decades in frequency (10-1-106 Hz) and in a wide temperature range from 373 K down to 173 K, accessing the dynamic observables both in liquid and glassy state. The dielectric response of the ionic system has been presented in the dynamic window of modulus formalism to understand the conductivity relaxation and its possible connection to the origin of localized motion. Two secondary relaxation processes appear below glass transition temperature. Our findings provide suitable interpretation on the nature of secondary Johari-Goldstein process describing the ion translation and orientation of dipoles in a combined approach using Ngai's coupling model. A nearly constant loss feature is witnessed at shorter times/lower temperatures. We also discuss the ac conductivity scaling behavior using Summerfield approach and random free energy barrier model which establish the time-temperature superposition principle. These experimental observations have fundamental importance on theoretical elucidation of the conductivity relaxation and glass transition phenomena in molten ionic conductors.

  3. Anti-inflammatory drugs interacting with Zn (II) metal ion based on thiocyanate and azide ligands: Synthesis, spectroscopic studies, DFT calculations and antibacterial assays

    NASA Astrophysics Data System (ADS)

    Chiniforoshan, Hossein; Tabrizi, Leila; Hadizade, Morteza; Sabzalian, Mohammad R.; Chermahini, Alireza Najafi; Rezapour, Mehdi

    2014-07-01

    Zinc (II) complexes with non-steroidal anti-inflammatory drugs (NSAIDs) naproxen (nap) and ibuprofen (ibu) were synthesized in the presence of nitrogen donor ligands (thiocyanate or azide). The complexes were characterized by elemental analysis, FT-IR, 1H NMR and UV-Vis spectroscopes. The binding modes of the ligands in complexes were established by means of molecular modeling of the complexes, and calculation of their IR, NMR and absorption spectra at DFT (TDDFT)/B3LYP level were studied. The experimental and calculated data verified monodentate binding through the carboxylic oxygen atoms of anti-inflammatory drugs in the zinc complexes. The calculated 1H, FT-IR and UV-Vis data are in better agreement with the experimental results, and confirm the predicted tetrahedral structures for the Zn (II) complexes. In addition to DFT calculations of complexes, natural bond orbital (NBO) was performed at B3LYP/6-31+G(d,p) level of theory. Biological studies showed the antibacterial activity of zinc complexes against Gram-positive and Gram-negative bacterial strains.

  4. Development of four-stage moving bed biofilm reactor train with a pre-denitrification configuration for the removal of thiocyanate and cyanate.

    PubMed

    Villemur, Richard; Juteau, Pierre; Bougie, Veronique; Ménard, Julie; Déziel, Eric

    2015-04-01

    Two trains (A and B) of four-stage moving bed biofilm reactors (MBBRs) were developed for the degradation of thiocyanate (SCN(-)), cyanate (OCN(-)) and ammonia (NH3). A pre-denitrification configuration was established in the first-stage reactor of the B train using SCN(-) and OCN(-) as the sole carbon source. SCN(-), OCN(-) and NH3 were completely removed in both trains. The highest removal of total nitrogen equivalent (total-N) occurred at a loading rate of 5.6 mg-N L(-1) h(-1). The pre-denitrification configuration resulted in increased total-N removal in the B train (62.6%) compared to the A train (38.5%). Thiobacillus spp. were the predominant bacteria in all MBBRs. Bacteria related to bioprocesses involving anaerobic ammonium oxidation were present in the B train, suggesting that part of nitrogen removal occurs via this pathway. Our results showed that the pre-denitrification configuration increases the efficiency of removal of total-N compounds in the SCN(-)/OCN(-)-degrading MBBR process.

  5. Glass transition dynamics and conductivity scaling in ionic deep eutectic solvents: The case of (acetamide + lithium nitrate/sodium thiocyanate) melts

    SciTech Connect

    Tripathy, Satya N. Wojnarowska, Zaneta; Knapik, Justyna; Paluch, Marian; Shirota, Hideaki; Biswas, Ranjit

    2015-05-14

    A detailed investigation on the molecular dynamics of ionic deep eutectic solvents (acetamide + lithium nitrate/sodium thiocyanate) is reported. The study was carried out employing dielectric relaxation spectroscopy covering seven decades in frequency (10{sup −1}-10{sup 6} Hz) and in a wide temperature range from 373 K down to 173 K, accessing the dynamic observables both in liquid and glassy state. The dielectric response of the ionic system has been presented in the dynamic window of modulus formalism to understand the conductivity relaxation and its possible connection to the origin of localized motion. Two secondary relaxation processes appear below glass transition temperature. Our findings provide suitable interpretation on the nature of secondary Johari-Goldstein process describing the ion translation and orientation of dipoles in a combined approach using Ngai’s coupling model. A nearly constant loss feature is witnessed at shorter times/lower temperatures. We also discuss the ac conductivity scaling behavior using Summerfield approach and random free energy barrier model which establish the time-temperature superposition principle. These experimental observations have fundamental importance on theoretical elucidation of the conductivity relaxation and glass transition phenomena in molten ionic conductors.

  6. Structural evidence of substrate specificity in mammalian peroxidases: structure of the thiocyanate complex with lactoperoxidase and its interactions at 2.4 A resolution.

    PubMed

    Sheikh, Ishfaq Ahmed; Singh, Amit Kumar; Singh, Nagendra; Sinha, Mau; Singh, S Baskar; Bhushan, Asha; Kaur, Punit; Srinivasan, Alagiri; Sharma, Sujata; Singh, Tej P

    2009-05-29

    The crystal structure of the complex of lactoperoxidase (LPO) with its physiological substrate thiocyanate (SCN(-)) has been determined at 2.4A resolution. It revealed that the SCN(-) ion is bound to LPO in the distal heme cavity. The observed orientation of the SCN(-) ion shows that the sulfur atom is closer to the heme iron than the nitrogen atom. The nitrogen atom of SCN(-) forms a hydrogen bond with a water (Wat) molecule at position 6'. This water molecule is stabilized by two hydrogen bonds with Gln(423) N(epsilon2) and Phe(422) oxygen. In contrast, the placement of the SCN(-) ion in the structure of myeloperoxidase (MPO) occurs with an opposite orientation, in which the nitrogen atom is closer to the heme iron than the sulfur atom. The site corresponding to the positions of Gln(423), Phe(422) oxygen, and Wat(6)' in LPO is occupied primarily by the side chain of Phe(407) in MPO due to an entirely different conformation of the loop corresponding to the segment Arg(418)-Phe(431) of LPO. This arrangement in MPO does not favor a similar orientation of the SCN(-) ion. The orientation of the catalytic product OSCN(-) as reported in the structure of LPO.OSCN(-) is similar to the orientation of SCN(-) in the structure of LPO.SCN(-). Similarly, in the structure of LPO.SCN(-).CN(-), in which CN(-) binds at Wat(1), the position and orientation of the SCN(-) ion are also identical to that observed in the structure of LPO.SCN.

  7. Ionic liquids-lithium salts pretreatment followed by ultrasound-assisted extraction of vitexin-4″-O-glucoside, vitexin-2″-O-rhamnoside and vitexin from Phyllostachys edulis leaves.

    PubMed

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

    2016-01-29

    An efficient method for the extraction of vitexin, vitexin-4″-O-glucoside, and vitexin-2″-O-rhamnoside from Phyllostachys edulis leaves comprises heat treatment using an ionic liquid-lithium salt mixture (using 1-butyl-3-methylimidazolium bromide as the solvent and lithium chloride as the additive), followed by ultrasound-assisted extraction. To obtain higher extraction yields, the effects of the relevant experimental parameters (including heat treatment temperature and time, relative amounts of 1-butyl-3-methylimidazolium bromide and lithium chloride, power and time of the ultrasound irradiation, and the liquid-solid ratio) are evaluated and response surface methodology is used to optimize the significant factors. The morphologies of the treated and untreated P. edulis leaves are studied by scanning electron microscopy. The improved extraction method proposed provides high extraction yield, good repeatability and precision, and has wide potential applications in the analysis of plant samples. PMID:26763300

  8. Fast Measurement of Methanol Concentration in Ionic Liquids by Potential Step Method

    PubMed Central

    Hainstock, Michael L.; Tang, Yijun

    2015-01-01

    The development of direct methanol fuel cells required the attention to the electrolyte. A good electrolyte should not only be ionic conductive but also be crossover resistant. Ionic liquids could be a promising electrolyte for fuel cells. Monitoring methanol was critical in several locations in a direct methanol fuel cell. Conductivity could be used to monitor the methanol content in ionic liquids. The conductivity of 1-butyl-3-methylimidazolium tetrafluoroborate had a linear relationship with the methanol concentration. However, the conductivity was significantly affected by the moisture or water content in the ionic liquid. On the contrary, potential step could be used in sensing methanol in ionic liquids. This method was not affected by the water content. The sampling current at a properly selected sampling time was proportional to the concentration of methanol in 1-butyl-3-methylimidazolium tetrafluoroborate. The linearity still stood even when there was 2.4 M water present in the ionic liquid. PMID:25802522

  9. Ionic liquids-lithium salts pretreatment followed by ultrasound-assisted extraction of vitexin-4″-O-glucoside, vitexin-2″-O-rhamnoside and vitexin from Phyllostachys edulis leaves.

    PubMed

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

    2016-01-29

    An efficient method for the extraction of vitexin, vitexin-4″-O-glucoside, and vitexin-2″-O-rhamnoside from Phyllostachys edulis leaves comprises heat treatment using an ionic liquid-lithium salt mixture (using 1-butyl-3-methylimidazolium bromide as the solvent and lithium chloride as the additive), followed by ultrasound-assisted extraction. To obtain higher extraction yields, the effects of the relevant experimental parameters (including heat treatment temperature and time, relative amounts of 1-butyl-3-methylimidazolium bromide and lithium chloride, power and time of the ultrasound irradiation, and the liquid-solid ratio) are evaluated and response surface methodology is used to optimize the significant factors. The morphologies of the treated and untreated P. edulis leaves are studied by scanning electron microscopy. The improved extraction method proposed provides high extraction yield, good repeatability and precision, and has wide potential applications in the analysis of plant samples.

  10. Ligand-assisted soft-chemical synthesis of self-assembled different shaped mesoporous Co3O4: efficient visible light photocatalysts.

    PubMed

    Roy, Mouni; Ghosh, Sourav; Naskar, Milan Kanti

    2015-04-21

    Mesoporous self-assembled cobalt oxide (Co3O4) of different shapes was synthesized by a facile soft-chemical process using cobalt nitrate, oxalic acid and phosphoric acid in the presence of cationic templates, cetyltrimethylammonium bromide, 1-butyl-3-methylimidazolium bromide, and pyridinium bromide at 75 °C/2 h followed by calcination at 300 °C. The effect of cationic templates of the samples on the physico-chemical properties, and the photocatalytic efficiency for the degradation of Chicago Sky Blue 6B was studied. Pyridinium bromide and 1-butyl-3-methylimidazolium bromide facilitated formation of particles with different shaped morphology compared to cetyltrimethylammonium bromide. The rod-like particles having higher surface area exhibited higher photocatalytic performance. PMID:25792483

  11. Carbon nanoparticle ionic liquid hybrids and their photoluminescence properties.

    PubMed

    Wei, Ying; Liu, Yang; Li, Haitao; He, Xiaodie; Zhang, Qingguo; Kang, Zhenhui; Lee, Shuit-Tong

    2011-06-01

    A fluorescent carbon nanoparticle ionic liquid hybrids (CNPIL) with high conductivity is synthesized by a facile one-step microwave method from ionic liquid 1-butyl-3-methylimidazolium glutamine salt and Glucose. This CNPIL exhibits excellent PL properties: bright and colorful PL covering the entire visible-NIR spectral range, up conversion PL properties, pH dependent and can be controlled by the reaction condition.

  12. Ionic liquid acceleration of solid-phase suzuki-miyaura cross-coupling reactions.

    PubMed

    Revell, Jefferson D; Ganesan, A

    2002-09-01

    [reaction: see text] Room-temperature ionic liquids promote various transition metal-catalyzed reactions in the solution phase. Here, for the first time, we show that these effects are translatable to solid-phase reactions. The Suzuki-Miyaura cross-coupling of 4-iodophenol immobilized on polystyrene-Wang resin with various arylboronic acids was significantly accelerated by the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF(4)(-)]).

  13. A selenium-based ionic liquid as a recyclable solvent for the catalyst-free synthesis of 3-selenylindoles.

    PubMed

    Zimmermann, Everton G; Thurow, Samuel; Freitas, Camilo S; Mendes, Samuel R; Perin, Gelson; Alves, Diego; Jacob, Raquel G; Lenardão, Eder J

    2013-04-05

    The ionic liquid 1-butyl-3-methylimidazolium methylselenite, [bmim][SeO2(OCH3)], was successfully used as solvent in the catalyst-free preparation of 3-arylselenylindoles by the reaction of indole with ArSeCl at room temperature. The products were obtained selectively in good yields without the need of any additive and the solvent was easily reused for several cycles with good results.

  14. Organo-niobate Ionic Liquids: Synthesis, Characterization and Application as Acid Catalyst in Pechmann Reactions

    PubMed Central

    Soares, Valerio C. D.; Alves, Melquizedeque B.; Souza, Ernesto R.; Pinto, Ivana O.; Rubim, Joel C.; Andrade, Carlos Kleber Z.; Suarez, Paulo A. Z.

    2007-01-01

    The combinations of 1-butyl-3-methylimidazolium chloride with NbCl5 yielded ionic mixtures with different melting point temperatures and acidity depending on the niobium molar fraction. The mixtures were characterized by thermal (DSC) and spectroscopic (FT-IR and 1H NMR) analysis. The Pechmann reactions of different phenols with ethylacetoacetate, producing coumarins, was used as model to evaluate the catalytic behavior of these mixtures as acid Lewis catalyst. These reactions were carried out using acidic mixtures of 60 mol%.

  15. Molecularly imprinted SPE coupled with HPLC for the selective separation and enrichment of alkyl imidazolium ionic liquids in environmental water samples.

    PubMed

    Xia, Gao; Jing, Fan; Guifen, Zhu; Xiaolong, Wang; Jianji, Wang

    2013-10-01

    A novel 1-butyl-3-methylimidazolium chloride ionic liquid surface imprinted solid-phase sorbent was synthesized. The as-prepared material was characterized by SEM, Brunauer-Emmett-Teller surface area analysis and Fourier Transform IR measurements. Then its adsorption properties for alkyl imidazolium ionic liquids, including adsorption capacities, adsorption kinetics, and properties of selective separation and enrichment were studied in detail. It was shown that the ionic liquid surface imprinted polymer exhibited high selective recognition characteristics for the imidazolium chloride ionic liquids with short alkyl chains (C(n)mimCl, n = 2, 4, 6, 8) and the adsorption equilibrium was achieved within 25 min. Various parameters were optimized for the 1-butyl-3-methylimidazolium chloride ionic liquid surface imprinted polymer SPE column, such as flow rate, eluent solvent, selectivity, and reusability of the column. Then, the SPE column coupled with HPLC was used for the determination of alkyl imidazolium ionic liquids. Experimental results showed that the existence of their structural analogs and common concomitants in environmental matrices did not affect the enrichment of 1-butyl-3-methyl imidazolium chloride ionic liquid. The average recoveries of 1-butyl-3-methylimidazolium chloride ionic liquid in spiked water samples were in the range of 92.0-102.0% with the RSD lower than 5.8%.

  16. Ionic liquids influence on the surface properties of electron beam irradiated wood

    NASA Astrophysics Data System (ADS)

    Croitoru, Catalin; Patachia, Silvia; Doroftei, Florica; Parparita, Elena; Vasile, Cornelia

    2014-09-01

    In this paper, the influence of three imidazolium-based ionic liquids (1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate and 1-hexyl-3-methylimidazolium chloride) on the structure and surface properties of sycamore maple (Acer pseudoplatanus) veneers submitted to electron beam irradiation with a dose of 50 kGy has been studied by using Fourier transform infrared spectroscopy, as well as image, scanning electron microscopy/SEM/EDX, atomic force microscopy and contact angle analysis. The experimental results have proven that the studied ionic liquids determine a better preservation of the structural features of wood (cellulose crystallinity index and lignin concentration on the surface) as well as some of surface properties such as surface energy, roughness, color upon irradiation with electron beam, in comparison with the reference wood, but surface composition is changed by treatment with imidazolium-based ionic liquids mainly with 1-butyl-3-methylimidazolium tetrafluoroborate. Also, under electron beam irradiation covalent bonding of the imidazolium moiety to wood determines a higher resistance to water penetration and spreading on the surface.

  17. Sound velocity dispersion in room temperature ionic liquids studied using the transient grating method.

    PubMed

    Fukuda, M; Terazima, M; Kimura, Y

    2008-03-21

    Sound velocity is determined by the transient grating method in a range from 10(6) to 10(10) Hz in three room temperature ionic liquids, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-butyl-3-methylimidazolium hexafluorophosphate, and N,N,N-trimethyl-N-propylammonium bis(trifluoromethanesulfonyl)imide. In all room temperature ionic liquids studied, the sound velocity increased with increasing frequency. The cause of this change is posited to be structural relaxation in the room temperature ionic liquids. Frequency dependence of the sound velocity is not reproduced by a simple Debye relaxation model. The sound velocity dispersion relation in 1-butyl-3-methylimidazolium hexafluorophosphate matches a Cole-Davidson function with parameters determined by a dielectric relaxation [C. Daguenet et al., J. Phys. Chem. B 110, 12682 (2006)], indicating that structural and reorientational relaxations are strongly coupled. Conversely, the sound velocity dispersions of the other two ionic liquids measured do not match those measured for dielectric relaxation, implying that structural relaxation is much faster than the reorientational relaxation. This difference is discussed in relation to the motilities of anions and cations. PMID:18361592

  18. Oligo-nuclear silver thiocyanate complexes with monodentate tertiary phosphine ligands, including novel 'cubane' and 'step' tetramer forms of AgSCN : PR3 (1:1)4.

    PubMed

    Bowmaker, Graham A; Di Nicola, Corrado; Effendy; Hanna, John V; Healy, Peter C; King, Scott P; Marchetti, Fabio; Pettinari, Claudio; Robinson, Ward T; Skelton, Brian W; Sobolev, Alexandre N; Tăbăcaru, Aurel; White, Allan H

    2013-01-01

    Adducts of a number of tertiary pnicogen ligands ER(3) (triphenyl-phosphine and -arsine (PPh(3),AsPh(3)), diphenyl,2-pyridylphosphine (PPh(2)py), tris(4-fluorophenyl)phosphine (P(C(6)H(4)-4F)(3)), tris(2-tolyl)phosphine (P(o-tol)(3)), tris(cyclohexyl)phosphine (PCy(3))), with silver(I) thiocyanate, AgSCN are structurally and spectroscopically characterized. The 1:3 AgSCN : ER(3) complexes structurally defined (for PPh(3),AsPh(3) (diversely solvated)) take the form [(R(3)E)(3)AgX], the thiocyanate X = NCS being N-bound, thus [(Ph(3)E)Ag(NCS)]. A 1:2 complex with PPh(2)py, takes the binuclear form [(pyPh(2)P)(2)Ag()Ag(PPh(2)py)(2)] with an eight-membered cyclic core. 1:1 complexes are defined with PPh(2)py, P(o-tol)(3) and PCy(3); binuclear forms [(R(3)P)Ag()Ag(PR(3))] are obtained with P(o-tol)(3) (two polymorphs), while novel isomeric tetranuclear forms, which may be envisaged as dimers of dimers, are obtained with PPh(2)py, and, as further polymorphs, with PCy(3); these latter may be considered as extensions of the 'cubane' and 'step' forms previously described for [(R(3)E)AgX](4) (X = halide) complexes. Solvent-assisted mechanochemical or solvent-assisted solid-state synthesis methods were employed in some cases, where complexes could not be obtained by conventional solution methods, or where such methods yielded a mixture of polymorphs unsuitable for solid-state spectroscopy. The wavenumbers of the ν(CN) bands in the IR spectra are in broad agreement with the empirical rule that distinguishes bridging from terminal bonding, but exceptions occur for compounds that have a double SCN bridged dimeric structure, and replacement of PPh(3) with PPh(2)py apparently causes a significant decrease in ν(CN) to well below the range expected for bridging SCN in these structures. (31)P CP MAS NMR spectra yield additional parameters that allow a correlation between the structures and spectra.

  19. Headspace sorptive solid phase microextraction (HS-SPME) combined with a spectrophotometry system: A simple glass devise for extraction and simultaneous determination of cyanide and thiocyanate in environmental and biological samples.

    PubMed

    Al-Saidi, H M; Al-Harbi, Sami A; Aljuhani, E H; El-Shahawi, M S

    2016-10-01

    A simple, low cost and efficient headspace sorptive solid phase microextraction (HS-SPME) method for determination of cyanide has been developed. The system comprises of a glass tube with two valves and a moveable glass slide fixed at its centre. It includes an acceptor phase polyurethane foam treated mercury (II) dithizonate [Hg(HDz)2-PUF] complex fixed inside by a septum cap in a cylindrical configuration (5.0cm length and 1.0cm diameter). The extraction is based upon the contact of the acceptor phase to the headspace and subsequently measuring the absorbance of the recovered mercury (II) dithizonate from PUFs sorbent. Unlike other HSSE, extraction and back - extractions was carried out in a closed system, thereby improving the analytical performance by preventing the analyte loss. Under the optimized conditions, a linear calibration plot in the range of 1.0-50.0µmolL(-1) was achieved with limits of detection (LOD) and quantification (LOQ) of 0.34, 1.2µmolL(-1) CN(-), respectively. Simultaneous analysis of cyanide and thiocyanate in saliva was also performed with satisfactory recoveries.

  20. Headspace sorptive solid phase microextraction (HS-SPME) combined with a spectrophotometry system: A simple glass devise for extraction and simultaneous determination of cyanide and thiocyanate in environmental and biological samples.

    PubMed

    Al-Saidi, H M; Al-Harbi, Sami A; Aljuhani, E H; El-Shahawi, M S

    2016-10-01

    A simple, low cost and efficient headspace sorptive solid phase microextraction (HS-SPME) method for determination of cyanide has been developed. The system comprises of a glass tube with two valves and a moveable glass slide fixed at its centre. It includes an acceptor phase polyurethane foam treated mercury (II) dithizonate [Hg(HDz)2-PUF] complex fixed inside by a septum cap in a cylindrical configuration (5.0cm length and 1.0cm diameter). The extraction is based upon the contact of the acceptor phase to the headspace and subsequently measuring the absorbance of the recovered mercury (II) dithizonate from PUFs sorbent. Unlike other HSSE, extraction and back - extractions was carried out in a closed system, thereby improving the analytical performance by preventing the analyte loss. Under the optimized conditions, a linear calibration plot in the range of 1.0-50.0µmolL(-1) was achieved with limits of detection (LOD) and quantification (LOQ) of 0.34, 1.2µmolL(-1) CN(-), respectively. Simultaneous analysis of cyanide and thiocyanate in saliva was also performed with satisfactory recoveries. PMID:27474290

  1. Template-free solution approach to synthesize CdS dendrites with SCN based ionic liquid

    SciTech Connect

    Li, Kangfeng; Li, Jiajia; Cheng, Xianyi; Liu, Weidong; Ying, Taokai

    2011-07-15

    Highlights: {yields} Template-free solution approach to synthesize CdS hierarchical dendrites. {yields} The 1-butyl-3-methlyimidazole thiocyanate ([BMIM][SCN]) plays doubly functional roles in the progress. {yields} The CdS hierarchical dendrites exhibit a more intense emission at 710 nm belongs to infrared band. -- Abstract: Cadmium sulfide dendrites were synthesized by a facile hydrothermal treatment from CdCl{sub 2} and ionic liquid 1-butyl-3-methlyimidazole thiocyanate acted both as sulfur source and surfactant. The product was characterized by means of X-ray powder diffraction and scanning electron microscopy. X-ray powder diffraction studies indicated that the product was well-crystallized hexagonal phase of CdS, and the scanning electron microscopy images showed that the obtained powders consisted of a wealth of well-defined CdS dendritic microstructures with a pronounced trunk and highly ordered branches. The UV-Vis and photoluminescence spectroscopy measurements were taken as well. The possible formation mechanism of CdS dendrites was simply proposed in the end.

  2. Dynamics of Loop 1 of Domain I in Human Serum Albumin WhenDissolved in Ionic Liquids

    SciTech Connect

    Page, Taylor; Kraut, Nadine; Page, Phillip; Baker, Gary A; Bright, Frank

    2009-01-01

    We report on the rotational reorientation dynamics associated with loop 1 of domain I within a large multidomain protein (human serum albumin, HSA) when it is dissolved in binary mixtures of ionic liquid (1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C4mim][Tf2N]), 1-butyl-3-methylimidazolium tetrafluoroborate ([C4mim][BF4]), or 1-butyl-3-methylimidazolium hexafluorophosphate ([C4mim][PF6])) and distilled deionized water (ddH2O) as a function of temperature and water loading. In IL/2% ddH2O (v/v) mixtures, loop 1 of domain I is more significantly denatured in comparison to the protein dissolved in aqueous solutions containing strong chemical denaturants (e.g., 8 M guanidine HCl (Gu HCl) or urea). As water loading increases, there is evidence for progressive refolding of loop 1 of domain I followed by recoupling with domains I, II, and III in the [C4mim][BF4]/ddH2O mixtures at 20 C. Above 30% (v/v) water, where domain I appears refolded, the Ac reporter molecule s semiangle steadily decreases from 35 to 20 with increasing water loading. From the perspective of domain I in HSA, this behavior is similar to the effects of dilution from 4 to 0 M Gu HCl in aqueous solution. Overall, these results lend insight into the tangle of biocatalytic and structural/dynamical mechanisms that enzymes may undergo in ionic liquid-based systems. It will be particularly motivating to extend this work to include enzyme-attuned ionic liquids shown to improve biocatalytic performance beyond that possible in the native (predominantly aqueous) setting.

  3. Dynamics of loop 1 of domain I in human serum albumin when dissolved in ionic liquids.

    PubMed

    Page, Taylor A; Kraut, Nadine D; Page, Phillip M; Baker, Gary A; Bright, Frank V

    2009-09-24

    We report on the rotational reorientation dynamics associated with loop 1 of domain I within a large multidomain protein (human serum albumin, HSA) when it is dissolved in binary mixtures of ionic liquid (1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C4mim][Tf2N]), 1-butyl-3-methylimidazolium tetrafluoroborate ([C4mim][BF4]), or 1-butyl-3-methylimidazolium hexafluorophosphate ([C4mim][PF6])) and distilled deionized water (ddH2O) as a function of temperature and water loading. In IL/2% ddH2O (v/v) mixtures, loop 1 of domain I is more significantly denatured in comparison to the protein dissolved in aqueous solutions containing strong chemical denaturants (e.g., 8 M guanidine HCl (Gu.HCl) or urea). As water loading increases, there is evidence for progressive refolding of loop 1 of domain I followed by recoupling with domains I, II, and III in the [C4mim][BF4]/ddH2O mixtures at 20 degrees C. Above 30% (v/v) water, where domain I appears refolded, the Ac reporter molecule's semiangle steadily decreases from 35 degrees to 20 degrees with increasing water loading. From the perspective of domain I in HSA, this behavior is similar to the effects of dilution from 4 to 0 M Gu.HCl in aqueous solution. Overall, these results lend insight into the tangle of biocatalytic and structural/dynamical mechanisms that enzymes may undergo in ionic liquid-based systems. It will be particularly motivating to extend this work to include enzyme-attuned ionic liquids shown to improve biocatalytic performance beyond that possible in the native (predominantly aqueous) setting.

  4. Pulse Radiolysis of Aqueous Thiocyanate Solution

    SciTech Connect

    Milosavljevic, Bratoljub H.; LaVerne, Jay A.

    2005-01-13

    The pulse radiolysis of N2O saturated aqueous solutions of KSCN was studied under neutral pH conditions. The observed optical absorption spectrum of the SCN• radical in solution is more complex than previously reported, but it is in good agreement with that measured in the gas phase. Kinetic traces at 330 nm and 472 nm corresponding to SCN• and (SCN)2•¯, respectively, were fit using a Monte Carlo simulation kinetic model. The rate coefficient for the oxidation of SCN¯ ions by OH radicals, an important reaction used in competition kinetics measurements, was found to be 1.4 ± 0.1 x 1010 M-1 s-1, about 30 % higher than the normally accepted value. A detailed discussion of the reaction mechanism is presented.

  5. 21 CFR 558.248 - Erythromycin thiocyanate.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 18.5 Chickens; growth promotion and feed efficiency ,061623 (ii) 9.25 to 18.5 Turkeys; growth promotion and feed efficiency For turkeys not over 12 weeks of age ,061623 (iii) 9.25 to 64.75 Swine...; withdraw 24 h before slaughter 3. Turkeys; as an aid in the prevention of chronic respiratory...

  6. 21 CFR 558.248 - Erythromycin thiocyanate.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... DRUGS, FEEDS, AND RELATED PRODUCTS NEW ANIMAL DRUGS FOR USE IN ANIMAL FEEDS Specific New Animal Drugs... disease during periods of stress Feed for 2 d before stress and 3 to 6 d after stress; withdraw 24 h...; withdraw 24 h before slaughter 3. Turkeys; as an aid in the prevention of chronic respiratory...

  7. 21 CFR 558.248 - Erythromycin thiocyanate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... disease during periods of stress Feed for 2 d before stress and 3 to 6 d after stress; withdraw 24 h... during periods of stress Feed for 2 d before stress and 3 to 6 d after stress (vi) 185 1. Chickens; as...

  8. Templated electrodeposition of silver nanowires in a nanoporous polycarbonate membrane from a nonaqueous ionic liquid electrolyte

    NASA Astrophysics Data System (ADS)

    Kazeminezhad, I.; Barnes, A. C.; Holbrey, J. D.; Seddon, K. R.; Schwarzacher, W.

    2007-03-01

    Template electrodeposition has been used to prepare a wide range of nanostructures but has generally been restricted to aqueous electrolytes. We report the deposition of silver nanowires in a commercial nuclear track-etched polycarbonate template from the nonaqueous ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]) using silver electrochemically dissolved from the anode. Transmission electron microscopy (TEM) shows that the nanowires have a very high aspect ratio with an average diameter of 80 nm and length of 5 μm. Ionic liquid electrolytes should greatly extend the range of metals that can be electrodeposited as nanowires using templates.

  9. Fabrication and Characterization of Polysaccharide Ion Gels with Ionic Liquids and Their Further Conversion into Value-Added Sustainable Materials

    PubMed Central

    Takada, Akihiko; Kadokawa, Jun-ichi

    2015-01-01

    A review of the fabrication of polysaccharide ion gels with ionic liquids is presented. From various polysaccharides, the corresponding ion gels were fabricated through the dissolution with ionic liquids. As ionic liquids, in the most cases, 1-butyl-3-methylimidazolium chloride has been used, whereas 1-allyl-3methylimidazolium acetate was specifically used for chitin. The resulting ion gels have been characterized by suitable analytical measurements. Characterization of a pregel state by viscoelastic measurement provided the molecular weight information. Furthermore, the polysaccharide ion gels have been converted into value-added sustainable materials by appropriate procedures, such as exchange with other disperse media and regeneration. PMID:25793912

  10. Microwave-assisted rapid conversion of carbohydrates into 5-hydroxymethylfurfural by ScCl3 in ionic liquids.

    PubMed

    Zhou, Xuanmu; Zhang, Zehui; Liu, Bing; Xu, Zheng; Deng, Kejian

    2013-06-28

    In this study, synthesis of HMF from carbohydrates was carried out in ionic liquids 1-butyl-3-methylimidazolium chloride ([Bmim]Cl) catalyzed by ScCl3 under microwave irradiation. Under the optimal reaction conditions, HMF was obtained in a high yield of 73.4% in 2 mins with the microwave power at 400 W. Compared with the conventional oil-bath heating manner, the use of microwave irradiation not only reduced reaction times from hours to minutes, but also improved HMF yield. This catalytic system could be reused several times without losing its catalytic activity. This efficient catalytic system will generate a promising application strategy for biomass transformation. PMID:23694706

  11. 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. PMID:27561513

  12. Lipid extraction from microalgae using a single ionic liquid

    DOEpatents

    Salvo, Roberto Di; Reich, Alton; Dykes, Jr., H. Waite H.; Teixeira, Rodrigo

    2013-05-28

    A one-step process for the lysis of microalgae cell walls and separation of the cellular lipids for use in biofuel production by utilizing a hydrophilic ionic liquid, 1-butyl-3-methylimidazolium. The hydrophilic ionic liquid both lyses the microalgae cell walls and forms two immiscible layers, one of which consists of the lipid contents of the lysed cells. After mixture of the hydrophilic ionic liquid with a suspension of microalgae cells, gravity causes a hydrophobic lipid phase to move to a top phase where it is removed from the mixture and purified. The hydrophilic ionic liquid is recycled to lyse new microalgae suspensions.

  13. Electrodeposition of Three Dimensionally Ordered Macroporous Germanium from Two Different Ionic Liquids.

    PubMed

    Hao, Jian; Zhao, Jiupeng; Zhang, Yiwen; An, Xiaokun; Liu, Xin; Li, Yao; Endres, Frank

    2016-01-01

    Three dimensionally ordered macroporous (3DOM) Ge films have been made via ordered polystyrene (PS) templates by electrodeposition from ionic liquids 1-Butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) amide and 1-Ethyl-3-methylimidazolium tris (pentafluoroethyl) trifluorophosphate at room temperature. We discuss the possibility of obtaining high quality 3DOM Ge films from two different ionic liquids by the simple and inexpensive template-assisted electrochemical pathway. Scanning electron microscopy confirms the quality of the samples, and the optical measurements demonstrate that 3DOM Ge made electrochemically shows photonic crystal behavior. Such a material has the potential to make 3DOM Ge feasible for electrical, optical applications and for photonic crystal solar cells.

  14. Effect of BMITFSI to the electrical properties of methycelloluse/chitosan/NH4TF-based polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Arifin, N. A.; Khiar, A. S. A.

    2015-12-01

    Blended polymer electrolyte of methylcellulose (MC) / chitosan with ammonium triflate (NH4TF) were prepared with different weight percentage of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BMITFSI) via solution casting technique. The film was characterized by impedance spectroscopy to measure its ionic conductivity. Samples with 45% of BMITFSI exhibit the highest conductivity of (3.98 +/- 2.84) x 10-4 Scm-1 at ambient. Dielectric data were analyzed by using complex permittivity and complex electrical modulus for the sample with highest conductivity. Dielectric data proves that the increase in conductivity is mainly due to the increase in number of charge carriers.

  15. A study of the time-resolved fluorescence spectrum and red edge effect of ANF in a room-temperature ionic liquid.

    PubMed

    Hu, Zhonghan; Margulis, Claudio J

    2006-06-15

    In a recent article, we have analyzed using molecular dynamics simulations the steady-state red edge effect (REE) observed by Samanta and co-workers when the fluorescent probe 2-amino-7-nitrofluorene (ANF) is photoexcited at different wavelengths in 1-butyl-3-methylimidazolium ([BMIM+]) hexafluorophosphate ([PF6-]). In this letter, we predict the time- and wavelength-dependent emission spectra of ANF in the same ionic solvent. From the analysis of our simulated data, we are able to derive an approximate time scale for reorganization of the solvent around the solute probe. The effect that slow varying local liquid environments have on the overall time-dependent signal is also discussed.

  16. 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.

  17. Homogeneous ionic liquid microextraction of the active constituents from fruits of Schisandra chinensis and Schisandra sphenanthera.

    PubMed

    Xiao, Yao; Zhang, Hanqi

    2012-01-27

    Homogeneous ionic liquid microextraction (HILME) was developed for the extraction of schizandrin, schisantherin A and deoxyschizandrin from Schisandra chinensis and Schisandra sphenanthera. 1-Butyl-3-methylimidazolium tetrafluoroborate ([C(4)MIM][BF(4)]) aqueous solution was used as extraction solvent, and ammonium hexafluorophosphate ([NH(4)][PF(6)]) was used as ion-pairing agent. 1-Butyl-3-methylimidazolium hexafluorophosphate ([C(4)MIM][PF(6)]), which is barely soluble in water, was formed in situ, and was used as sample solution. High-performance liquid chromatography (HPLC) was employed for separation and determination of the analytes. The calibration curve showed good linear relationship (r>0.9998). The recoveries were between 69.71% and 88.33% with RSDs lower than 4.86%. External standard method was adopted in the proposed method, and internal standard method was applied for the evaluation of the proposed method. The two methods were compared and the results indicated that the proposed method was acceptable and simple. The HILME is free of volatile organic solvents, and represents lower expenditures of sample, extraction time and solvent, compared with ultrasonic and Soxhlet extraction. There was no obvious difference in the extraction yields of active constitutions obtained by the three extraction methods.

  18. Conversion of hexose into 5-hydroxymethylfurfural in imidazolium ionic liquids with and without a catalyst.

    PubMed

    Cao, Quan; Guo, Xingcui; Yao, Shengxi; Guan, Jing; Wang, Xiaoyan; Mu, Xindong; Zhang, Dongke

    2011-05-15

    Conversion of fructose and glucose into 5-hydroxymethylfurfural (HMF) was investigated in various imidazolium ionic liquids, including 1-butyl-3-methylimidazolium chloride (BmimCl), 1-hexyl-3-methylimidazolium chloride (HmimCl), 1-octyl-3-methylimidazolium chloride (OmimCl), 1-benzyl-3-methylimidazolium chloride (BemimCl), 1-Butyl-2,3-dimethylimidazolium chloride (BdmimCl), and 1-butyl-3-methylimidazolium p-toluenesulfonate (BmimPS). The acidic C-2 hydrogen of imidazolium cations was shown to play a major role in the dehydration of fructose in the absence of a catalyst, such as sulfuric acid or CrCl(3). Both the alkyl groups of imidazolium cations and the type of anions affected the reactivity of the carbohydrates. Although, except BmimCl and BemimCl, other four ionic liquids could only achieve not more than 25% HMF yields without an additional catalyst, 60-80% HMF yields were achieved in HmimCl, BdmimCl, and BmimPS in the presence of sulfuric acid or CrCl(3) in sufficient quantities.

  19. Screening of lignan patterns in Schisandra species using ultrasonic assisted temperature switch ionic liquid microextraction followed by UPLC-MS/MS analysis.

    PubMed

    Dong, Wei; Yu, Shuijing; Deng, Yangwu; Pan, Tao

    2016-01-01

    The ultrasonic assisted temperature-switch ionic liquid microextraction (UATS-ILME) has been successfully applied in extracting of seven lignans from Schisandra. 1-Butyl-3-methylimidazolium tetrafluoroborate ([C4MIM][BF4]) aqueous solution was selected for extracting the target analytes in raw material at 80°C. The lignans were deposited into a single drop by in situ forming 1-butyl-3-methylimidazolium hexafluorophosphate ([C4MIM][PF6]) by cooling down to 0°C and centrifuging for 10min. The extracts were analyzed by ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) in a robust multiple-reaction monitoring (MRM) mode in five minutes. Meanwhile, the proposed method was validated and successfully applied to the determination of seven lignans in twelve Schisandra species. The results indicated that UATS-ILME combined with UPLC-MS/MS is a powerful and practical tool, which has great potential for comprehensive quality control of herbal medicines. PMID:26625336

  20. Heteroatom-Containing Porous Carbons Derived from Ionic Liquid-Doped Alkali Organic Salts for Supercapacitors.

    PubMed

    Zhu, Jingyue; Xu, Dan; Qian, Wenjing; Zhang, Jinyu; Yan, Feng

    2016-04-13

    A simple strategy for the synthesis of heteroatom-doped porous carbon materials (CMs) via using ionic liquid (IL)-doped alkali organic salts as small molecular precursors is developed. Doping of alkali organic salts (such as sodium glutamate, sodium tartrate, and sodium citrate) with heteroatoms containing ILs (including 1-butyl-3-methylimidazolium chlorine and 3-butyl-4-methythiazolebromination) not only incorporates the heteroatoms into the carbon frameworks but also highly improves the carbonization yield, as compared with that of either alkali organic salts or ILs as precursors. The porous structure of CMs can be tuned by adjusting the feed ratio of ILs. The porous CMs derived from 1-butyl-3-methylimidazolium chlorine-doped sodium glutamate exhibit high charge storage capacity with a specific capacitance of 287 F g(-1) and good stability over 5000 cycles in 6 m KOH at a current density of 1 A g(-1) for supercapacitors. This strategy opens a simple and efficient method for the synthesis of heteroatom-doped porous CMs. PMID:26869577

  1. Heats of vaporization of room temperature ionic liquids by tunable vacuum ultraviolet photoionization

    SciTech Connect

    Chambreau, Steven D.; Vaghjiani, Ghanshyam L.; To, Albert; Koh, Christine; Strasser, Daniel; Kostko, Oleg; Leone, Stephen R.

    2009-11-25

    The heats of vaporization of the room temperature ionic liquids (RTILs) N-butyl-N-methylpyrrolidinium bistrifluorosulfonylimide, N-butyl-N-methylpyrrolidinium dicyanamide, and 1-butyl-3-methylimidazolium dicyanamide are determined using a heated effusive vapor source in conjunction with single photon ionization by a tunable vacuum ultraviolet synchrotron source. The relative gas phase ionic liquid vapor densities in the effusive beam are monitored by clearly distinguished dissociative photoionization processes via a time-of-flight mass spectrometer at a tunable vacuum ultraviolet beamline 9.0.2.3 (Chemical Dynamics Beamline) at the Advanced Light Source synchrotron facility. Resulting in relatively few assumptions, through the analysis of both parent cations and fragment cations, the heat of vaporization of N-butyl-N-methylpyrrolidinium bistrifluorosulfonylimide is determined to be Delta Hvap(298.15 K) = 195+-19 kJ mol-1. The observed heats of vaporization of 1-butyl-3-methylimidazolium dicyanamide (Delta Hvap(298.15 K) = 174+-12 kJ mol-1) and N-butyl-N-methylpyrrolidinium dicyanamide (Delta Hvap(298.15 K) = 171+-12 kJ mol-1) are consistent with reported experimental values using electron impact ionization. The tunable vacuum ultraviolet source has enabled accurate measurement of photoion appearance energies. These appearance energies are in good agreement with MP2 calculations for dissociative photoionization of the ion pair. These experimental heats of vaporization, photoion appearance energies, and ab initio calculations corroborate vaporization of these RTILs as intact cation-anion ion pairs.

  2. The Highly Selective and Near-Quantitative Conversion of Glucose to 5-Hydroxymethylfurfural Using Ionic Liquids

    PubMed Central

    Eminov, Sanan; Brandt, Agnieszka; Wilton-Ely, James D. E. T.

    2016-01-01

    A number of ionic liquids have been shown to be excellent solvents for lignocellulosic biomass processing, and some of these are particularly effective in the production of the versatile chemical building block 5-hydroxymethylfurfural (HMF). In this study, the production of HMF from the simple sugar glucose in ionic liquid media is discussed. Several aspects of the selective catalytic formation of HMF from glucose have been elucidated using metal halide salts in two distinct ionic liquids, 1-butyl-3-methylimidazolium chloride and 1-butyl-3-methylimidazolium hydrogen sulfate as well as mixtures of these, revealing key features for accelerating the desired reaction and suppressing byproduct formation. The choice of ionic liquid anion is revealed to be of particular importance, with low HMF yields in the case of hydrogen sulfate-based salts, which are reported to be effective for HMF production from fructose. The most successful system investigated in this study led to almost quantitative conversion of glucose to HMF (90% in only 30 minutes using 7 mol% catalyst loading at 120°C) in a system which is selective for the desired product, has low energy intensity and is environmentally benign. PMID:27711238

  3. Extraction of arsenic in a soil of the blackfoot disease endemic area with ionic liquids

    NASA Astrophysics Data System (ADS)

    Liao, C.-Y.; Wang, H. Paul; Peng, C.-Y.; Kang, H.-Y.; Wei, Y.-L.

    2009-04-01

    Speciation of arsenic in the soil of the old blackfoot disease endemic area in the Southern Taiwan has been studied by X-ray absorption near edge structural (XANES) and extended X-ray absorption fine structural (EXAFS) spectroscopy. Experimentally, at the contact time of 30-180 min, 30-40% of As(III) and 40-60% of As(V) in the soil can be extracted with a room temperature ionic liquid (RTIL) [BMI][BF4] (1-butyl-3-methylimidazolium tetrafluoroborate). For the relatively hydrophobic RTIL [BMI][PF6] (1-butyl-3-methylimidazolium hexafluorophosphate), on the contrary, 10-15% of As(III) and 20-25% of As(V) can be extracted. By XANES, it is found that an enhanced oxidation of the extracted As(III) (As(III)→As(V)) in the RTIL may occur during the extraction processes. The refined EXAFS spectra also indicate that the bond distances of As(III)-N and As(V)-N in the arsenic-extracted RTILs are 1.76-1.78 and 1.68-1.70

  4. Extraction of arsenic from a soil in the blackfoot disease endemic area with ionic liquids

    NASA Astrophysics Data System (ADS)

    Liao, Chang-Yu; Peng, Ching-Yu; Wang, Hong-Chung; Kang, Hsu-Ya; Paul Wang, H.

    2011-10-01

    Speciation of arsenic extracted with room temperature ionic liquids (RTILs) ([bmim][BF 4] (1-butyl-3-methylimidazolium tetrafluoroborate) and [bmim][PF 6] (1-butyl-3-methylimidazolium hexafluorophosphate)) from an As-humic acid (As-HA) complex contaminated soil (As-HA/soil) in a blackfoot disease endemic area has been studied by X-ray absorption (near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS)) spectroscopy. About 45% of arsenic in the As-HA/soil can be extracted with [bmim][BF 4] while the relatively less hydrophilic [bmim][PF 6] extracts 25% of arsenic. The extracted arsenic in the [bmim][BF 4] and [bmim][PF 6] from the As-HA/soil possesses mainly As(III) species, suggesting that at least two reaction paths may be involved in the extraction process: (1) splitting of As-HA and (2) reduction of As(V) to As(III). The refined EXAFS spectra also indicate that the As(III) extracted in the RTILs possesses the AsO 2- structure, which has the As-O bond distances of 1.77-1.79 Å and coordination numbers of 4.0-4.2.

  5. Lignin dissolution in dialkylimidazolium-based ionic liquid-water mixtures.

    PubMed

    Wang, Yantao; Wei, Ligang; Li, Kunlan; Ma, Yingchong; Ma, Ningning; Ding, Shan; Wang, Linlin; Zhao, Deyang; Yan, Bing; Wan, Wenying; Zhang, Qian; Wang, Xin; Wang, Junmei; Li, Hui

    2014-10-01

    Lignin dissolution in dialkylimidazolium-based ionic liquid (IL)-water mixtures (40wt%-100wt% IL content) at 60°C was investigated. The IL content and type are found to considerably affect lignin solubility. For the IL-water mixtures except 1-butyl-3-methylimidazolium tetrafluoroborate ([C4C1im]BF4), the maximum lignin solubility can be achieved at 70wt% IL content. Lignin solubility in IL-water mixtures with different cations follows the order 1-butyl-3-methylimidazolium ([C4C1im](+))>1-hexyl-3-methylimidazolium ([C6C1im](+))>1-ethyl-3-methylimidazolium ([C2C1im](+))>1-octyl-3-methylimidazolium ([C8C1im](+))>1-butyl-3-ethylimidazolium ([C4C2im](+))>1-butyl-3-propylimidazolium ([C4C3im](+)). For IL mixtures with different anions, lignin solubility decreases in the following order: methanesulfonate (MeSO3(-))>acetate (MeCO2(-))>bromide (Br(-))>dibutylphosphate (DBP(-)). Evaluation using the theory of Hansen solubility parameter (HSP) is consistent with the experimental results, suggesting that HSP can aid in finding the appropriate range of IL content for IL-water mixtures. However, HSP cannot be used to evaluate the effect of IL type on lignin solubility. PMID:25164342

  6. Extraction of ranitidine and nizatidine with using imidazolium ionic liquids prior spectrophotometric and chromatographic detection.

    PubMed

    Kiszkiel, Ilona; Starczewska, Barbara; Leśniewska, Barbara; Późniak, Patrycja

    2015-03-15

    A new extraction medium was proposed for liquid-liquid extraction of the histamine H2 receptor antagonists ranitidine (RNT) and nizatidine (NZT). The ionic liquids with low vapor pressure and favorable solvating properties for a range of compounds such as 1-butyl-3-methylimidazolium hexafluorophosphate [C4mim][PF6] and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [C4mim][Tf2N] were tested for isolation of analytes. The extraction parameters of RNT and NZT, namely, amount of ionic liquid, pH of sample solution, shaking and centrifugation time were optimized. The isolation processes were performed with 1 mL of the ionic liquids. The extracted samples (pH values near 4) were shaken at 1750 rpm. The influence of interfering substances on the efficiency of extraction process was also studied. Methods for the histamine H2 receptor antagonists (ranitidine and nizatidine) determination after their separation using imidazolium ionic liquids by high performance liquid chromatography (HPLC) combined with UV spectrophotometry were developed. The application of ionic liquids in extraction step allows for selective isolation of analytes from aqueous matrices and their preconcentration. The above methods were applied to the determination of RNT and NZT in environmental samples (river water and wastewater after treatment).

  7. Ionic liquid-linked dual magnetic microextraction of lead(II) from environmental samples prior to its micro-sampling flame atomic absorption spectrometric determination.

    PubMed

    Yilmaz, Erkan; Soylak, Mustafa

    2013-11-15

    A novel and rapid microextraction approach termed as ionic liquid-linked dual magnetic microextraction (IL-DMME), was developed for the atomic absorption spectrometric determination of lead. The developed method based on a combination of dispersive liquid-liquid microextraction (DLLME) and dispersive micro solid-phase extraction (D-μ-SPE). In the first DLLME step, 1-butyl-3-methylimidazolium hexafluorophosphate [C4mim][PF6], was selected to extract the lead-pyrrolidine-dithiocarbamate (Pb-PDC) complex from sample solution by the assistance of vortex agitator. After the first step, fifty milligrams of Fe3O4 magnetic nanoparticles (MNPs) were added to extraction of the ionic liquid and Pb-PDC complex in aqueous solution. The effective factors in proposed IL-DMME procedure, including volume of 1-butyl-3-methylimidazolium hexafluorophosphate, amount of Fe3O4 magnetic nanoparticles, vortex time, amount of ammonium pyrrolidinedithiocarbamate, sample volume and matrix effect were optimized in details. Under the optimal conditions, the method present has low detection limit (0.57 μg L(-1)), high preconcentration factor (160) and good repeatability (<7.5%, n=10). The accuracy of the developed method was evaluated by the analysis of the certified reference materials and addition-recovery tests. The method was successfully applied to the determination of lead in water, plant and hair samples.

  8. Correlation between the fluorescent response of microfluidity probes and the water content and viscosity of ionic liquid and water mixtures.

    PubMed

    Pandey, Siddharth; Fletcher, Kristin A; Baker, Sheila N; Baker, Gary A

    2004-07-01

    Accurate data on transport properties such as viscosity are essential in plant and process design involving ionic liquids. In this study, we determined the absolute viscosity of the ionic liquid + water system at water mole fractions from 0 to 0.25 for three 1-alkyl-3-methylimidazolium ionic liquids: 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium bis(trifluoromethane sulfonyl)imide and 1-ethyl-3-methylimidazolium bis(trifluoromethane sulfonyl)imide. In each case, the excimer to monomer ratio for 1,m-bis(1-pyrenyl)alkanes (m= 3 or 10) was found to increase linearly with the mole fraction of water. Of the probes studied only PRODAN and rhodamine 6G, both of which have the ability to participate in hydrogen bonding, exhibited Perrin hydrodynamic behavior in the lower viscosity bis(trifluoromethane sulfonyl)imides. As a result, these probes allow for the extrapolation of the absolute viscosity of the ionic liquid mixture from the experimental fluorescence steady-state polarization values.

  9. Ionic liquids entrapped in reverse micelles as nanoreactors for bimolecular nucleophilic substitution reaction. Effect of the confinement on the chloride ion availability.

    PubMed

    Blach, Diana; Pessêgo, Marcia; Silber, Juana J; Correa, N Mariano; García-Río, Luis; Falcone, R Darío

    2014-10-21

    In this work was explored how the confinement of two ionic liquids (ILs), 1-butyl-3-methylimidazolium chloride (bmimCl) and 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF4), inside toluene/benzyl-n-hexadecyldimethylammonium chloride (BHDC) reverse micelles (RMs) affects the Cl(-) nucleophilicity on the bimolecular nucleophilic substitution (SN2) reaction between this anion and dimethyl-4-nitrophenylsulfonium trifluoromethanesulfonate. The results obtained show that, upon confinement, the ionic interactions between the ILs with the cationic surfactant polar head group and the surfactant counterion modify substantially the performance of both ILs as solvents. In toluene/BHDC/bmimCl RMs, the Cl(-) interacts strongly with bmim(+) (and/or BHD(+)) in such a way that its nucleophilicity is reduced in comparison with neat IL. In toluene/BHDC/bmimBF4 RMs, an ionic exchange equilibrium produces segregation of bmim(+) and BF4(-) ions, changing the composition of the RMs interface and affecting dramatically the Cl(-) availability. These results show the versatility of this kind of organized system to alter the ionic organization and influence on reaction rate when used as nanoreactors.

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

    SciTech Connect

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

    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 efficiencies and selectivities of Th-227/Ac-225 are also presented in this article.

  11. Alkylation of Methyl Linoleate with Propene in Ionic Liquids in the Presence of Metal Salts.

    PubMed

    Pomelli, Christian Silvio; Ghilardi, Tiziana; Chiappe, Cinzia; de Angelis, Alberto Renato; Calemma, Vincenzo

    2015-01-01

    Vegetable oils and fatty acid esters are suitable precursor molecules for the production of a variety of bio-based products and materials, such as paints and coatings, plastics, soaps, lubricants, cosmetics, pharmaceuticals, printing inks, surfactants, and biofuels. Here, we report the possibility of using Lewis acidic ionic liquids (ILs) to obtain polyunsaturated ester dimerization-oligomerization and/or, in the presence of another terminal alkene (propene), co-polymerization. In particular, we have tested the Lewis acidic mixtures arising from the addition of a proper amount of GaCl₃ (Χ > 0.5) to two chloride-based (1-butyl-3-methylimidazolium chloride, [bmim]Cl, and 1-butylisoquinolium chloride, [BuIsoq]Cl) or by dissolution of a smaller amount of Al(Tf₂N)₃ (Χ = 0.1) in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [bmim][Tf₂N]. On the basis of product distribution studies, [bmim][Tf₂N]/Al(Tf₂N)₃ appears the most suitable medium in which methyl linoleate alkylation with propene can compete with methyl linoleate or propene oligomerization. PMID:26690107

  12. Application of cold-induced aggregation microextraction as a fast, simple, and organic solvent-free method for the separation and preconcentration of Se(IV) in rice and various water samples.

    PubMed

    Rahnama, Reyhaneh; Abed, Zinat

    2014-07-01

    The developed method is based on cold-induced aggregation microextraction of Se(IV) using the 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid as an extractant followed by spectrophotometry determination. The extraction of Se(IV) was performed in the presence of dithizone as the complexing agent. In this method, a very small amount of 1-butyl-3-methylimidazolium hexafluorophosphate was added to the sample solution containing Se-dithizone complex. Then, the solution was kept in a thermostated bath at 50 °C for 4 min. Subsequently, the solution was cooled in an ice bath and a cloudy solution was formed. After centrifuging, the extractant phase was analyzed using a spectrophotometric detection method. Some important parameters that might affect the extraction efficiency were optimized (HCl, 0.6 mol L(-1); dithizone, 4.0 × 10(-6) mol L(-1); ionic liquid, 100 μL). Under the optimum conditions, good linear relationship, sensitivity, and reproducibility were obtained. The limit of detection (LOD) (3Sb/m) was 1.5 μg L(-1), and the relative standard deviation (RSD) was 1.2 % for 30 μg L(-1) of Se(IV). The linear range was obtained in the range of 5-60 μg L(-1). It was satisfactory to analyze rice and various water samples. PMID:24590231

  13. Insight into dissolution mechanism of cellulose in [C4mim][CH3COO]/DMSO solvent by 13C NMR spectra

    NASA Astrophysics Data System (ADS)

    Xu, Airong; Zhang, Yibo

    2015-05-01

    Recently, it has been reported that 1-butyl-3-methylimidazolium acetate/dimethyl sulfoxide ([C4mim][CH3COO]/DMSO) can efficiently dissolve cellulose at room temperature. In the present study, 13C NMR measurements of 1-butyl-3-methylimidazolium acetate [C4mim][CH3COO] and cellulose were carried out in [C4mim][CH3COO]/DMSO-d6 (Deuterated dimethyl sulfoxide)/cellulose solution to directly reveal the possible dissolution mechanism of cellulose in true [C4mim][CH3COO]/DMSO solvent. The results indicate that both cation and anion of [C4mim][CH3COO] in [C4mim][CH3COO]/DMSO solvent dominate cellulose dissolution, and DMSO mainly serves to dissociate the ion pairs in [C4mim][CH3COO] into solvated cations and anions. Moreover, the hydrogen bonding interaction of anion of [C4mim][CH3COO] with cellulose hydroxyl proton is much stronger than that of cation of [C4mim][CH3COO] with cellulose hydroxyl oxygen.

  14. Ionic liquid-linked dual magnetic microextraction of lead(II) from environmental samples prior to its micro-sampling flame atomic absorption spectrometric determination.

    PubMed

    Yilmaz, Erkan; Soylak, Mustafa

    2013-11-15

    A novel and rapid microextraction approach termed as ionic liquid-linked dual magnetic microextraction (IL-DMME), was developed for the atomic absorption spectrometric determination of lead. The developed method based on a combination of dispersive liquid-liquid microextraction (DLLME) and dispersive micro solid-phase extraction (D-μ-SPE). In the first DLLME step, 1-butyl-3-methylimidazolium hexafluorophosphate [C4mim][PF6], was selected to extract the lead-pyrrolidine-dithiocarbamate (Pb-PDC) complex from sample solution by the assistance of vortex agitator. After the first step, fifty milligrams of Fe3O4 magnetic nanoparticles (MNPs) were added to extraction of the ionic liquid and Pb-PDC complex in aqueous solution. The effective factors in proposed IL-DMME procedure, including volume of 1-butyl-3-methylimidazolium hexafluorophosphate, amount of Fe3O4 magnetic nanoparticles, vortex time, amount of ammonium pyrrolidinedithiocarbamate, sample volume and matrix effect were optimized in details. Under the optimal conditions, the method present has low detection limit (0.57 μg L(-1)), high preconcentration factor (160) and good repeatability (<7.5%, n=10). The accuracy of the developed method was evaluated by the analysis of the certified reference materials and addition-recovery tests. The method was successfully applied to the determination of lead in water, plant and hair samples. PMID:24148489

  15. Evaluation of synergistic enantioseparation systems with chiral spirocyclic ionic liquids as additives by capillary electrophoresis.

    PubMed

    Zhang, Yanjie; Du, Shuaijing; Feng, Zijie; Du, Yingxiang; Yan, Zhi

    2016-04-01

    In recent years, chiral ionic liquids (CILs) have attracted more and more attention in the field of enantioseparation. In this study, two novel spirocyclic chiral ionic liquids, 1-butyl-3-methylimidazolium(T-4)-bis[(2S)-2-(hydroxy-κO)-3-methylbutanoato-κO]borate (BMIm(+)BLHvB(-)) and 1-butyl-3-methylimidazolium (T-4)-bis[(αS)-α-(hydroxy-κO)-4-methylbenzeneacetato-κO]borate (BMIm(+)BSMB(-)), were applied for the first time in capillary electrophoresis (CE) to establish synergistic systems for enantiomeric separation. Significantly improved separations of five tested analytes were observed in the CILs synergistic systems based on three β-cyclodextrin derivatives (CD), compared with conventional single CD separation systems. Several principal parameters such as CILs concentration, cyclodextrin concentration, buffer pH, and applied voltage were systematically investigated with BMIm(+)BLHvB(-)/hydroxypropyl-β-CD selected as a model system to optimize the enantioseparation. Molecular modeling was applied to further demonstrate the chiral recognition mechanism of the CILs/hydroxypropyl-β-CD synergistic system, which showed a good agreement with the experimental results. PMID:26894758

  16. Ionic liquids for improving the extraction of NSAIDs in water samples using dispersive liquid-liquid microextraction by high performance liquid chromatography-diode array-fluorescence detection.

    PubMed

    Toledo-Neira, Carla; Álvarez-Lueje, Alejandro

    2015-03-01

    A rapid, sensitive and efficient analytical method based on the use of ionic liquids for determination of non-steroidal anti-inflammatory drugs (NSAIDs) in water samples was developed. High-performance liquid chromatography equipped with a diode array and fluorescence detector was used for quantification of ketoprofen, ibuprofen and diclofenac in tap and river water samples. This new method relies on the use of two ionic liquids with multiple functionalities: one functions as an extraction solvent (1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]), and the other changes the polarity in the aqueous medium (1-butyl-3-methylimidazolium tetrafluoroborate, ([BMIM][BF4]). Factors such as the type and volume of the ILs and dispersive solvent, sample volume, and centrifugation time were investigated and optimized. The optimized method exhibited good precision, with relative standard deviation values between 2% and 3%, for the three NSAIDs. Limits of detection achieved for all of the analytes were between 17 and 95 ng mL(-1), and the recoveries ranged from 89% to 103%. Furthermore, the enrichment factors ranged from 49 to 57. The proposed method was successfully applied to the analysis of NSAIDs in tap and river water samples.

  17. Screening of lignan patterns in Schisandra species using ultrasonic assisted temperature switch ionic liquid microextraction followed by UPLC-MS/MS analysis.

    PubMed

    Dong, Wei; Yu, Shuijing; Deng, Yangwu; Pan, Tao

    2016-01-01

    The ultrasonic assisted temperature-switch ionic liquid microextraction (UATS-ILME) has been successfully applied in extracting of seven lignans from Schisandra. 1-Butyl-3-methylimidazolium tetrafluoroborate ([C4MIM][BF4]) aqueous solution was selected for extracting the target analytes in raw material at 80°C. The lignans were deposited into a single drop by in situ forming 1-butyl-3-methylimidazolium hexafluorophosphate ([C4MIM][PF6]) by cooling down to 0°C and centrifuging for 10min. The extracts were analyzed by ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) in a robust multiple-reaction monitoring (MRM) mode in five minutes. Meanwhile, the proposed method was validated and successfully applied to the determination of seven lignans in twelve Schisandra species. The results indicated that UATS-ILME combined with UPLC-MS/MS is a powerful and practical tool, which has great potential for comprehensive quality control of herbal medicines.

  18. Determination of atenolol in human plasma using ionic-liquid-based ultrasound-assisted in situ solvent formation microextraction followed by high-performance liquid chromatography.

    PubMed

    Zeeb, Mohsen; Farahani, Hadi; Papan, Mohammad Kazem

    2016-06-01

    An efficient analytical method called ionic-liquid-based ultrasound-assisted in situ solvent formation microextraction followed by high-performance liquid chromatography was developed for the determination of atenolol in human plasma. A hydrophobic ionic liquid (1-butyl-3-methylimidazolium hexafluorophosphate) was formed by the addition of a hydrophilic ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate) to a sample solution containing an ion-pairing agent during microextraction. The analyte was extracted into the ionic liquid phase while the microextraction solvent was dispersed throughout the sample by utilizing ultrasound. The sample was then centrifuged, and the extracting phase retracted into the microsyringe and injected to liquid chromatography. After optimization, the calibration curve showed linearity in the range of 2-750 ng/mL with the regression coefficient corresponding to 0.998. The limits of detection (S/N = 3) and quantification (S/N = 10) were 0.5 and 2 ng/mL, respectively. A reasonable relative recovery range of 90-96.7% and satisfactory intra-assay (4.8-5.1%, n = 6) and interassay (5.0-5.6%, n = 9) precision along with a substantial sample clean-up demonstrated good performance of the procedure. It was applied for the determination of atenolol in human plasma after oral administration and some pharmacokinetic data were obtained.

  19. Thiocyanate supplementation decreases atherosclerotic plaque in mice expressing human myeloperoxidase.

    PubMed

    Morgan, P E; Laura, R P; Maki, R A; Reynolds, W F; Davies, M J

    2015-06-01

    Elevated levels of the heme enzyme myeloperoxidase (MPO) are associated with adverse cardiovascular outcomes. MPO predominantly catalyzes formation of the oxidants hypochlorous acid (HOCl) from Cl(-), and hypothiocyanous acid (HOSCN) from SCN(-), with these anions acting as competitive substrates. HOSCN is a less powerful and more specific oxidant than HOCl, and selectively targets thiols; such damage is largely reversible, unlike much HOCl-induced damage. We hypothesized that increased plasma SCN(-), and hence HOSCN formation instead of HOCl, may decrease artery wall damage. This was examined using high-fat fed atherosclerosis-prone LDLR(-/-) mice transgenic for human MPO, with and without SCN(-) (10 mM) added to drinking water. Serum samples, collected fortnightly, were analyzed for cholesterol, triglycerides, thiols, MPO, and SCN(-); study-long exposure was calculated by area under the curve (AUC). Mean serum SCN(-) concentrations were elevated in the supplemented mice (200-320 μM) relative to controls (< 120 μM). Normalized aortic root plaque areas at sacrifice were 26% lower in the SCN(-)-supplemented mice compared with controls (P = 0.0417), but plaque morphology was not appreciably altered. Serum MPO levels steadily increased in mice on the high-fat diet, however, comparison of SCN(-)-supplemented versus control mice showed no significant changes in MPO protein, cholesterol, or triglyceride levels; thiol levels were decreased in supplemented mice at one time-point. Plaque areas increased with higher cholesterol AUC (r = 0.4742; P = 0.0468), and decreased with increasing SCN(-) AUC (r = - 0.5693; P = 0.0134). These data suggest that increased serum SCN(-) levels, which can be achieved in humans by dietary manipulation, may decrease atherosclerosis burden.

  20. Thiocyanate supplementation decreases atherosclerotic plaque in mice expressing human myeloperoxidase

    PubMed Central

    Morgan, P. E.; Laura, R. P.; Maki, R. A.; Reynolds, W. F.; Davies, M. J.

    2015-01-01

    Elevated levels of the heme enzyme myeloperoxidase (MPO) are associated with adverse cardiovascular outcomes. MPO predominantly catalyzes formation of the oxidants hypochlorous acid (HOCl) from Cl−, and hypothiocyanous acid (HOSCN) from SCN−, with these anions acting as competitive substrates. HOSCN is a less powerful and more specific oxidant than HOCl, and selectively targets thiols; such damage is largely reversible, unlike much HOCl-induced damage. We hypothesized that increased plasma SCN−, and hence HOSCN formation instead of HOCl, may decrease artery wall damage. This was examined using high-fat fed atherosclerosis-prone LDLR−/− mice transgenic for human MPO, with and without SCN− (10 mM) added to drinking water. Serum samples, collected fortnightly, were analyzed for cholesterol, triglycerides, thiols, MPO and SCN−; study-long exposure was calculated by area under the curve (AUC). Mean serum SCN− concentrations were elevated in the supplemented mice (200-320 μM) relative to controls (<120 μM). Normalized aortic root plaque areas at sacrifice were 26% lower in the SCN−-supplemented mice compared to controls (P=0.0417), but plaque morphology was not appreciably altered. Serum MPO levels steadily increased in mice on the high-fat diet, however, comparison of SCN−- supplemented vs. control mice showed no significant changes in MPO protein, cholesterol or triglyceride levels; thiol levels were decreased in supplemented mice at one time-point. Plaque areas increased with higher cholesterol AUC (r=0.4742; P=0.0468), and decreased with increasing SCN− AUC (r=−0.5693; P=0.0134). These data suggest that increased serum SCN− levels, which can be achieved in humans by dietary manipulation, may decrease atherosclerosis burden. PMID:25812586

  1. Reactions of Thiocyanate Ions with Acid: A Laboratory Experiment.

    ERIC Educational Resources Information Center

    Glidewell, Christopher; And Others

    1984-01-01

    Background information, procedures, and typical results are provided for a three-part experiment involving reactions of potassium thiocynate (KNCS) with sulfuric acid. The experiment represents the final stage of structured work prior to students' research projects during their final year. (JM)

  2. Environment of the thiocyanate ion in aqueous solutions

    SciTech Connect

    Lyashchenko, A.K.; Lileev, A.S.

    1985-10-01

    A comparison of the thermodynamic hydration characteristics and mobility data for a number of ions has shown that the SCN/sup -/ ion is a weakly hydrated ion. A Model for the insertion of this ion into the structure of water has been proposed. It has been shown that its coordination number with respect to water is equal to 6. The formation of species of the type Zn(SCN)/sub 2/ and Ca(SCN)/sup +/ over a broad range of solution concentrations has been postulated for the Zn/sup 2 +/ and Ca/sup 2 +/ ions.

  3. Peroxidase-Thiocyanate-Peroxide Antibacterial System Does Not Damage DNA

    PubMed Central

    White, William E.; Pruitt, Kenneth M.; Mansson-Rahemtulla, Britta

    1983-01-01

    The hypothiocyanite ion (OSCN-) is a normal component of human saliva. It is a highly reactive oxidizing agent, and at concentrations above the values normally found in human saliva, it inhibits the growth and metabolism of oral bacteria. This finding has led to the suggestion that antibacterial properties of human saliva might be enhanced in vivo by appropriate supplements which elevate OSCN- concentrations. Since DNA is sensitive to oxidizing agents (hydrogen peroxide attacks nucleosides), high concentrations of OSCN- in human saliva might damage DNA and produce deleterious effects on the oral mucosa. In the present study, the effect of high OSCN- concentrations on several mutagen-sensitive Salmonella typhimurium strains was determined. These strains are used to detect base-pair substitutions and frameshift mutations. We also studied the effects of OSCN- on a Saccharomyces cerevisiae (yeast) strain commonly employed as a test cell for evaluating the potential of a compound to produce gene conversion, mitotic crossing-over, or reverse mutation. By recording the UV spectra of mixtures of calf thymus DNA and OSCN-, we explored the possible in vitro reactions of this oxidizing agent with eucaryotic genetic material. Our results show that, at concentrations above 10 μM, OSCN- is toxic for the tested Salmonella typhimurium strains. The mutant strains with defects in cell wall lipopolysaccharides are killed more readily by OSCN- than is the strain lacking these defects. However, OSCN- was not mutagenic for any of the tested strains. Saccharomyces cerevisiae was not affected by OSCN- even at concentrations above 800 μM. Calf thymus DNA was not oxidized by OSCN-. We conclude that the elevated concentrations of OSCN- required to produce antibacterial effects in the human mouth pose no threat to the genetic material of host tissues. PMID:6340603

  4. Nacre-like calcium carbonate controlled by ionic liquid/graphene oxide composite template.

    PubMed

    Yao, Chengli; Xie, Anjian; Shen, Yuhua; Zhu, Jinmiao; Li, Hongying

    2015-06-01

    Nacre-like calcium carbonate nanostructures have been mediated by an ionic liquid (IL)-graphene oxide (GO) composite template. The resultant crystals were characterized by scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectroscopy, and X-ray powder diffractometry (XRD). The results showed that either 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM]BF4) or graphene oxide can act as a soft template for calcium carbonate formation with unusual morphologies. Based on the time-dependent morphology changes of calcium carbonate particles, it is concluded that nacre-like calcium carbonate nanostructures can be formed gradually utilizing [BMIM]BF4/GO composite template. During the process of calcium carbonate formation, [BMIM]BF4 acted not only as solvents but also as morphology templates for the fabrication of calcium carbonate materials with nacre-like morphology. Based on the observations, the possible mechanisms were also discussed.

  5. Application of a nanostructured sensor based on NiO nanoparticles modified carbon paste electrode for determination of methyldopa in the presence of folic acid

    NASA Astrophysics Data System (ADS)

    Fouladgar, Masoud; Ahmadzadeh, Saeid

    2016-08-01

    A new method for determination of methyldopa in the presence of folic acid has been described in this work. This method is based on modification of carbon paste electrode with NiO nanoparticles and an ionic liquid (1-Butyl-3-methylimidazolium hexafluorophosphate). Electrochemical studies showed that on the surface of modified electrode, oxidation current of methyldopa has been enhanced and shifted to negative potentials. The fabricated electrode exhibited a linear response to concentration of methyldopa from 0.1 to 700.0 μmol L-1. The sensitivity of the modified electrode to methyldopa not changed in the presence of folic acid and simultaneous or independent measurements of them are possible. The performance of proposed method was investigated by determination of methyldopa in real samples.

  6. Ionic liquid as a promising biobased green solvent in combination with microwave irradiation for direct biodiesel production.

    PubMed

    Wahidin, Suzana; Idris, Ani; Shaleh, Sitti Raehanah Muhamad

    2016-04-01

    The wet biomass microalgae of Nannochloropsis sp. was converted to biodiesel using direct transesterification (DT) by microwave technique and ionic liquid (IL) as the green solvent. Three different ionic liquids; 1-butyl-3-metyhlimidazolium chloride ([BMIM][Cl], 1-ethyl-3-methylimmidazolium methyl sulphate [EMIM][MeSO4] and 1-butyl-3-methylimidazolium trifluoromethane sulfonate [BMIM][CF3SO3]) and organic solvents (hexane and methanol) were used as co-solvents under microwave irradiation and their performances in terms of percentage disruption, cell walls ruptured and biodiesel yields were compared at different reaction times (5, 10 and 15 min). [EMIM][MeSO4] showed highest percentage cell disruption (99.73%) and biodiesel yield (36.79% per dried biomass) after 15 min of simultaneous reaction. The results demonstrated that simultaneous extraction-transesterification using ILs and microwave irradiation is a potential alternative method for biodiesel production. PMID:26851899

  7. Development of Ionic Liquid Modified Disposable Graphite Electrodes for Label-Free Electrochemical Detection of DNA Hybridization Related to Microcystis spp.

    PubMed

    Sengiz, Ceren; Congur, Gulsah; Erdem, Arzum

    2015-01-01

    In this present study, ionic liquid (1-butyl-3-methylimidazolium hexafluorophosphate (IL)) modified pencil graphite electrode (IL-PGEs) was developed for electrochemical monitoring of DNA hybridization related to Microcystis spp. (MYC). The characterization of IL-PGEs was performed using microscopic and electrochemical techniques. DNA hybridization related to MYC was then explored at the surface of IL-PGEs using differential pulse voltammetry (DPV) technique. After the experimental parameters were optimized, the sequence-selective DNA hybridization related to MYC was performed in the case of hybridization between MYC probe and its complementary DNA target, noncomplementary (NC) or mismatched DNA sequence (MM), or and in the presence of mixture of DNA target: NC (1:1) and DNA target: MM (1:1).

  8. Electrical, structural, thermal and electrochemical properties of corn starch-based biopolymer electrolytes.

    PubMed

    Liew, Chiam-Wen; Ramesh, S

    2015-06-25

    Biopolymer electrolytes containing corn starch, lithium hexafluorophosphate (LiPF6) and ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate (BmImPF6) are prepared by solution casting technique. Temperature dependence-ionic conductivity studies reveal Vogel-Tamman-Fulcher (VTF) relationship which is associated with free volume theory. Ionic liquid-based biopolymer electrolytes show lower glass transition temperature (Tg) than ionic liquid-free biopolymer electrolyte. X-ray diffraction (XRD) studies demonstrate higher amorphous region of ionic liquid-added biopolymer electrolytes. In addition, the potential stability window of the biopolymer electrolyte becomes wider and stable up to 2.9V. Conclusively, the fabricated electric double layer capacitor (EDLC) shows improved electrochemical performance upon addition of ionic liquid into the biopolymer electrolyte. The specific capacitance of EDLC based on ionic liquid-added polymer electrolyte is relatively higher than that of ionic liquid-free polymer electrolyte as depicted in cyclic voltammogram. PMID:25839815

  9. Performance of Liquid Phase Exfoliated Graphene As Electrochemical Double Layer Capacitors Electrodes

    NASA Astrophysics Data System (ADS)

    Huffstutler, Jacob; Wasala, Milinda; Richie, Julianna; Winchester, Andrew; Ghosh, Sujoy; Kar, Swastik; Talapatra, Saikat

    2014-03-01

    We will present the results of our investigations of electrochemical double layer capacitors (EDLCs) or supercapacitors (SC) fabricated using liquid-phase exfoliated graphene. Several electrolytes, such as aqueous potassium hydroxide KOH (6M), ionic 1-Butyl-3-methylimidazolium hexafluorophosphate [BMIM][PF6], and ionic 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate[BMP][FAP] were used. These EDLC's show good performance compared to other carbon nanomaterials based EDLC's devices. We found that the liquid phase exfoliated graphene based devices possess specific capacitance values as high as 262 F/g, when used with ionic liquid electrolyte[BMP][FAP], with power densities (~ 454 W/kg) and energy densities (~ 0.38Wh/kg). Further, these devices indicated rapid charge transfer response even without the use of any binders or specially prepared current collectors. A detailed electrochemical impedance spectroscopy analysis in order to understand the phenomenon of charge storage in these materials will be presented.

  10. Sensitive determination of Amaranth in drinks by highly dispersed CNT in graphene oxide "water" with the aid of small amounts of ionic liquid.

    PubMed

    Wang, Meiling; Sun, Yinlu; Yang, Xiongbo; Zhao, Jianwei

    2015-07-15

    Graphene oxide (GO) is a pH-dependent amphiphile. In this paper, it was found that carbon nanotubes (CNTs) can be highly dispersed in graphene oxide "water" with the aid of prototype ionic liquid of 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]). The introduction of [BMIM][PF6] not only can minimize the defects of poor electrical conductivity of GO, but also can improve the dispersibility of CNT in water. Hence, a new composite of CNT/GO-[BMIM][PF6] with high dispersibility and strong conductivity was presented for the first time and employed in the sensitive determination of Amaranth in soft drinks. The detection limit achieved (0.1 nM) is much lower than the guideline values in soft drinks. The ease of preparation, low background current, high sensitivity and stability can create novel avenues and applications for fabricating robust sensors for determination of other azo dyes in foods.

  11. Ionic liquid-based aqueous two-phase system, a sample pretreatment procedure prior to high-performance liquid chromatography of opium alkaloids.

    PubMed

    Li, Shehong; He, Chiyang; Liu, Huwei; Li, Kean; Liu, Feng

    2005-11-01

    An ionic liquid, 1-butyl-3-methylimidazolium chloride ([C4 mim]Cl)/salt aqueous two-phase systems (ATPS) was presented as a simple, rapid and effective sample pretreatment technique coupled with high-performance liquid chromatography (HPLC) for analysis of the major opium alkaloids in Pericarpium papaveris. To find optimal conditions, the partition behaviors of codeine and papaverine in ionic liquid/salt aqueous two-phase systems were investigated. Various factors were considered systematically, and the results indicated that both the pH value and the salting-out ability of salt had great influence on phase separation. The recoveries of codeine and papaverine were 90.0-100.2% and 99.3-102.0%, respectively, from aqueous samples of P. papaveris by the proposed method. PMID:16143571

  12. Molecular dynamics simulation of the behaviour of water in nano-confined ionic liquid-water mixtures

    NASA Astrophysics Data System (ADS)

    Docampo-Álvarez, B.; Gómez-González, V.; Montes-Campos, H.; Otero-Mato, J. M.; Méndez-Morales, T.; Cabeza, O.; Gallego, L. J.; Lynden-Bell, R. M.; Ivaništšev, V. B.; Fedorov, M. V.; Varela, L. M.

    2016-11-01

    This work describes the behaviour of water molecules in 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid under nanoconfinement, between graphene sheets. By means of molecular dynamics simulations, the adsorption of water molecules at the graphene surface is studied. A depletion of water molecules in the vicinity of the neutral and negatively charged graphene surfaces, and their adsorption at the positively charged surface are observed in line with the preferential hydration of the ionic liquid anions. The findings are appropriately described using a two-level statistical model. The confinement effect on the structure and dynamics of the mixtures is thoroughly analyzed using the density and the potential of mean force profiles, as well as by the vibrational densities of the states of water molecules near the graphene surface. The orientation of water molecules and the water-induced structural transitions in the layer closest to the graphene surface are also discussed.

  13. Application of Ionic Liquids in the Microwave-Assisted Extraction of Proanthocyanidins from Larix gmelini Bark

    PubMed Central

    Yang, Lei; Sun, Xiaowei; Yang, Fengjian; Zhao, Chunjian; Zhang, Lin; Zu, Yuangang

    2012-01-01

    Ionic liquid based, microwave-assisted extraction (ILMAE) was successfully applied to the extraction of proanthocyanidins from Larix gmelini bark. In this work, in order to evaluate the performance of ionic liquids in the microwave-assisted extraction process, a series of 1-alkyl-3-methylimidazolium ionic liquids with different cations and anions were evaluated for extraction yield, and 1-butyl-3-methylimidazolium bromide was selected as the optimal solvent. In addition, the ILMAE procedure for the proanthocyanidins was optimized and compared with other conventional extraction techniques. Under the optimized conditions, satisfactory extraction yield of the proanthocyanidins was obtained. Relative to other methods, the proposed approach provided higher extraction yield and lower energy consumption. The Larix gmelini bark samples before and after extraction were analyzed by Thermal gravimetric analysis, Fourier-transform infrared spectroscopy and characterized by scanning electron microscopy. The results showed that the ILMAE method is a simple and efficient technique for sample preparation. PMID:22606036

  14. Metsulfuron-methyl-based herbicidal ionic liquids.

    PubMed

    Pernak, Juliusz; Niemczak, Michał; Shamshina, Julia L; Gurau, Gabriela; Głowacki, Grzegorz; Praczyk, Tadeusz; Marcinkowska, Katarzyna; Rogers, Robin D

    2015-04-01

    Ten sulfonylurea-based herbicidal ionic liquids (HILs) were prepared by combining the metsulfuron-methyl anion with various cation types including quaternary ammonium ([bis(2-hydroxyethyl)methyloleylammonium](+), [2-hydroxyethyltrimethylammonium](+)), pyridinium ([1-dodecylpyridinium](+)), piperidinium ([1-methyl-1-propylpiperidinium](+)), imidazolium ([1-allyl-3-methylimidazolium](+), [1-butyl-3-methylimidazolium](+)), pyrrolidinium ([1-butyl-1-methylpyrrolidinium](+)), morpholinium ([4-decyl-4-methylmorpholinium](+)), and phosphonium ([trihexyltetradecylphosphonium](+) and [tetrabutylphosphonium](+)). Their herbicidal efficacy was studied in both greenhouse tests and field trials. Preliminary results for the greenhouse tests showed at least twice the activity for all HILs when compared to the activity of commercial Galmet 20 SG, with HILs with phosphonium cations being the most effective. The results of two-year field studies showed significantly less enhancement of activity than observed in the greenhouse; nonetheless, it was found that the herbicidal efficacy was higher than that of the commercial analog, and efficacy varied depending on the plant species. PMID:25734891

  15. 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. PMID:27112846

  16. Preparation of polyhedral oligomeric silsesquioxane based imprinted monolith.

    PubMed

    Li, Fang; Chen, Xiu-Xiu; Huang, Yan-Ping; Liu, Zhao-Sheng

    2015-12-18

    Polyhedral oligomeric silsesquioxane (POSS) was successfully applied, for the first time, to prepare imprinted monolithic column with high porosity and good permeability. The imprinted monolithic column was synthesized with a mixture of PSS-(1-Propylmethacrylate)-heptaisobutyl substituted (MA 0702), naproxon (template), 4-vinylpyridine, and ethylene glycol dimethacrylate, in ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM]BF4). The influence of synthesis parameters on the retention factor and imprinting effect, including the amount of MA 0702, the ratio of template to monomer, and the ratio of monomer to crosslinker, was investigated. The greatest imprinting factor on the imprinted monolithic column prepared with MA 0702 was 22, about 10 times higher than that prepared in absence of POSS. The comparisons between MIP monoliths synthesized with POSS and without POSS were made in terms of permeability, column efficiency, surface morphology and pore size distribution. In addition, thermodynamic and Van Deemter analysis were used to evaluate the POSS-based MIP monolith.

  17. Cellulase-producing bacteria from Thai higher termites, Microcerotermes sp.: enzymatic activities and ionic liquid tolerance.

    PubMed

    Taechapoempol, Kitipong; Sreethawong, Thammanoon; Rangsunvigit, Pramoch; Namprohm, Weerachart; Thamprajamchit, Bandhit; Rengpipat, Sirirat; Chavadej, Sumaeth

    2011-05-01

    The three highest hydrolysis-capacity-value isolates of Bacillus subtilis (A 002, M 015, and F 018) obtained from Thai higher termites, Microcerotermes sp., under different isolation conditions (aerobic, anaerobic, and anaerobic/aerobic) were tested for cellulase activities--FPase, endoglucanase, and β-glucosidase--at 37 °C and pH 7.2 for 24 h. Their tolerance to an ionic liquid, 1-butyl-3-methylimidazolium chloride ([BMIM]Cl), was also investigated. The results showed that the isolate M 015 provided the highest endoglucanase activity whereas the highest FPase and β-glucosidase activities were observed for the isolate F 018. The isolate F 018 also showed the highest tolerance to [BMIM]Cl in the range of 0.1-1.0 vol.%. In contrast, the isolate A 002 exhibited growth retardation in the presence of 0.5-1.0 vol.% [BMIM]Cl.

  18. Evaluation of a hydrophilic ionic liquid as a salting-out phase separation agent to a water-tetrahydrofuran homogeneous system for aqueous biphasic extraction separation.

    PubMed

    Hirayama, Naoki; Higo, Takaaki; Imura, Hisanori

    2012-01-01

    The use of a hydrophilic ionic liquid (IL), 1-butyl-3-methylimidazolium chloride (C(4)mimCl), as a salting-out phase separation agent to a water-tetrahydrofuran homogeneous system was studied for possible applications to novel aqueous biphasic extraction separation. The IL showed a salting-out phase-separation ability. Also, differences in the polarity between the formed two phases were smaller than that when using NaCl as a salting-out agent. This result suggested that C(4)mimCl remaining in water-rich phase acts not only as a salting-out agent, but also a component of a mixed-solvent. Possible uses of C(4)mimCl/NaCl mixed salting-out agent system were also discussed.

  19. Salting-out effects in aqueous ionic liquid solutions: cloud-point temperature shifts.

    PubMed

    Trindade, Joana R; Visak, Zoran P; Blesic, Marijana; Marrucho, Isabel M; Coutinho, João A P; Lopes, José N Canongia; Rebelo, Luis P N

    2007-05-10

    The effects of the addition of three inorganic salts, namely, NaCl, Na(2)SO(4), and Na(3)PO(4), on the liquid-liquid (L-L) phase diagram of aqueous solutions containing the model ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate, [bmim][BF(4)], were investigated. All three inorganic salts trigger salting-out effects, leading to significant upward shifts of the L-L demixing temperatures of the systems. The magnitude of the shifts depends on both the water-structuring nature of the salt and its concentration; that is, the effects are correlated with the ionic strength of the solution and the Gibbs free energy of hydration of the inorganic salt. The pH effect and the occurrence of salt precipitation in concentrated solutions are also discussed.

  20. Homogeneous esterification of xylan-rich hemicelluloses with maleic anhydride in ionic liquid.

    PubMed

    Peng, Xin-Wen; Ren, Jun-Li; Sun, Run-Cang

    2010-12-13

    Generation of bioenergy, new functional polymers, or chemicals and biomaterials from hemicelluloses are important uses for biomass. In this paper, a novel functional biopolymer with carbon-carbon double bond and carboxyl groups was prepared by a homogeneous esterification of xylan-rich hemicelluloses (XH) with maleic anhydride in 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) ionic liquid using LiOH as catalyst. The biopolymers with degrees of substitution (DS) between 0.095 and 0.75 were accessible in a completely homogeneous system by changing reaction temperature, reaction time, the dosage of catalyst, and the molar ratio of maleic anhydride to anhydroxylose unit in XH. Results obtained from FT-IR and (13)C NMR spectroscopies confirmed the structure of hemicellulosic derivatives with carbon-carbon double bond and carboxyl groups, implying an efficient method to prepare a novel and important functional biopolymer for biomaterials.

  1. The first molecular level monitoring of carbohydrate conversion to 5-hydroxymethylfurfural in ionic liquids. B2O3--an efficient dual-function metal-free promoter for environmentally benign applications.

    PubMed

    Khokhlova, Elena A; Kachala, Vadim V; Ananikov, Valentine P

    2012-04-01

    The mechanistic nature of the conversion of carbohydrates to the sustainable platform chemical 5-hydroxymethylfurfural (5-HMF) was revealed at the molecular level. A detailed study of the key sugar units involved in the biomass conversion process has shown that the simple dissolution of fructose in the ionic liquid 1-butyl-3-methylimidazolium chloride significantly changes the anomeric composition and favors the formation of the open fructoketose form. A special NMR approach was developed for the determination of molecular structures and monitoring of chemical reactions directly in ionic liquids. The transformation of glucose to 5-HMF has been followed in situ through the detection of intermediate species. A new environmentally benign, easily available, metal-free promoter with a dual functionality (B(2)O(3)) was developed for carbohydrate conversion to 5-HMF. PMID:22359390

  2. Two-dimensional ultrafast vibrational spectroscopy of azides in ionic liquids reveals solute-specific solvation.

    PubMed

    Dutta, Samrat; Ren, Zhe; Brinzer, Thomas; Garrett-Roe, Sean

    2015-10-28

    The stereochemistry and the reaction rates of bimolecular nucleophilic substitution reactions involving azides in ionic liquids are governed by solute-solvent interactions. Two-dimensional ultrafast vibrational spectroscopy (2D-IR) shows that the picosecond dynamics of inorganic azides are substantially slower than organic azides in a series of homologous imidazolium ionic liquids. In water, both organic and inorganic azides spectrally diffuse with a ∼2 ps time constant. In the aprotic solvent tetrahydrofuran, both kinds of azides spectrally diffuse on a timescale >5 ps. In ionic liquids, like 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF4]), organic azides spectrally diffuse with a 2-4 ps time constant, and inorganic azides spectrally diffuse with a >40 ps time constant. Such a striking difference suggests that neutral (organic) and charged (inorganic) azides are incorporated in the ionic liquids with different solvation structures.

  3. Supported Ionic Liquid Membranes and Ion-Jelly® Membranes with [BMIM][DCA]: Comparison of Its Performance for CO2 Separation

    PubMed Central

    Couto, Ricardo; Neves, Luísa; Simões, Pedro; Coelhoso, Isabel

    2015-01-01

    In this work, a supported ionic liquid membrane (SILM) was prepared by impregnating a PVDF membrane with 1-butyl-3-methylimidazolium dicyanamide ([BMIM][DCA]) ionic liquid. This membrane was tested for its permeability to pure gases (CO2, N2 and O2) and ideal selectivities were calculated. The SILM performance was also compared to that of Ion-Jelly® membranes, a new type of gelled membranes developed recently. It was found that the PVDF membrane presents permeabilities for pure gases similar or lower to those presented by the Ion-Jelly® membranes, but with increased ideal selectivities. This membrane presents also the highest ideal selectivity (73) for the separation of CO2 from N2 when compared with SILMs using the same PVDF support but with different ionic liquids. PMID:25594165

  4. Temperature effects on the capacitance of an imidazolium-based ionic liquid on a graphite electrode: a molecular dynamics simulation.

    PubMed

    Liu, Xiaohong; Han, Yining; Yan, Tianying

    2014-08-25

    Temperature-dependent electric double layer (EDL) and differential capacitance-potential (C(d)-U) curves of the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM(+)/PF6(-)) were studied on a graphite electrode by molecular dynamics simulations. It was found that all C(d)-U curves were asymmetric camel-shaped with higher C(d) at negative polarization, attributed to the specific adsorption of BMIM(+). In addition, the maxima of Cd at the negative polarization decrease monotonically with temperature due to the thicker EDL, whereas at the positive polarization they gradually increase from 450 to 550 K and decrease at 600 K. Such temperature effects at positive polarization may be understood in terms of the competition between two aspects: the weakening specific adsorption of BMIM(+) allows more effective screening to the positive charge and overall increasing EDL thickness. Although the former dominates from 450 to 550 K, the latter becomes dominant at 600 K.

  5. Comparison of some new pretreatment methods for second generation bioethanol production from wheat straw and water hyacinth.

    PubMed

    Guragain, Yadhu Nath; De Coninck, Joelle; Husson, Florence; Durand, Alain; Rakshit, Sudip Kumar

    2011-03-01

    Pretreatment of lignocellulosic residues like water hyacinth (WH) and wheat straw (WS) using crude glycerol (CG) and ionic liquids (IL) pretreatment was evaluated and compared with conventional dilute acid pretreatment (DAT) in terms of enzymatic hydrolysis yield and fermentation yield of pretreated samples. In the case of WS, 1-butyl-3-methylimidazolium acetate pretreatment was found to be the best method. The hydrolysis yields of glucose and total reducing sugars were 2.1 and 3.3 times respectively higher by IL pretreatment than DAT, while it was 1.4 and 1.9 times respectively higher with CG pretreatment. For WH sample, CG pretreatment was as effective as DAT and more effective than IL pretreatment regarding hydrolysis yield. The fermentation inhibition was not noticeable with both types of pretreatment methods and feedstocks. Besides, CG pretreatment was found as effective as pure glycerol pretreatment for both feedstocks. This opens up an attractive economic route for the utilization of CG. PMID:21273061

  6. Separation of Lignin from Corn Stover Hydrolysate with Quantitative Recovery of Ionic Liquid

    PubMed Central

    Underkofler, Kaylee A.; Teixeira, Rodrigo E.; Pietsch, Stephen A.; Knapp, Kurtis G.; Raines, Ronald T.

    2015-01-01

    Abundant lignocellulosic biomass could become a source of sugars and lignin, potential feedstocks for the now emergent bio-renewable economy. The production and conversion of sugars from biomass have been well-studied, but far less is known about the production of lignin that is amenable to valorization. Here we report the isolation of lignin generated from the hydrolysis of biomass dissolved in the ionic liquid 1-butyl-3-methylimidazolium chloride. We show that lignin can be isolated from the hydrolysate slurry by simple filtration or centrifugation, and that the ionic liquid can be recovered quantitatively by a straightforward wash with water. The isolated lignin is not only free from ionic liquid, but also lacks cellulosic residues and is substantially depolymerized, making it a promising feedstock for valorization by conversion into fuels and chemicals. PMID:25866701

  7. Morphology-controlled synthesis of nanostructured zinc hydroxide fluoride via a microwave-assisted ionic liquid route

    NASA Astrophysics Data System (ADS)

    Zhang, Songtao; Zheng, Mingbo; Song, Jiakui; Li, Nianwu; Lu, Hongling; Cao, Jieming

    2014-12-01

    Zinc hydroxide fluoride (Zn(OH)F) with multiform morphologies such as flower-like particles, pumpkin-like aggregates, and hollow orange-like aggregates are prepared by a microwave-assisted ionic liquid method. During synthesis, microwave irradiation accelerates the reaction rate and shortens the reaction time. 1-Butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF4]) or 1-2-hydroxylethyl-3-methylimidazolium tetrafluoroborate ([C2OHmim][BF4]) is used as both reactant and template. Experimental results indicate that the morphology evolution of Zn(OH)F is mainly controlled by the concentration of zinc acetate solution. A possible mechanism underlying the formation of nanostructured Zn(OH)F with diverse morphologies is proposed. Furthermore, nanoporous ZnO is obtained by the thermal decomposition of as-prepared Zn(OH)F in air, and the morphology is well retained.

  8. Fluorescence spectroscopic analysis of the interaction of papain with ionic liquids.

    PubMed

    Fan, Yunchang; Yan, Jinlong; Zhang, Sheli; Li, Junhai; Chen, Dong; Duan, Peigao

    2012-10-01

    The interaction between papain and two typical ionic liquids (ILs), 1-octyl-3-methylimidazolium chloride ([C(8)mim]Cl) and 1-butyl-3-methylimidazolium chloride ([C(4)mim]Cl), was investigated by using fluorescence spectroscopy technique at a pH value of 7.4. The results suggested that ILs could quench the intrinsic fluorescence of papain probably via a static quenching mechanism. The binding constants were determined by employing the fluorescence quenching method. They were very small compared with that of volatile organic solvents, indicating that only very weak interaction between ILs and papain existed. The Gibbs free energy change (∆G), enthalpy change (∆H), and entropy change (∆S) during the interaction of papain and ILs were estimated. Negative values of these parameters indicated that the interaction between ILs and papain was a spontaneous process, also implying that hydrogen bonding and van der Waals forces played important roles in the interaction processes. PMID:22798189

  9. 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

  10. Fabrication of normally-off AlGaN/GaN metal–insulator–semiconductor high-electron-mobility transistors by photo-electrochemical gate recess etching in ionic liquid

    NASA Astrophysics Data System (ADS)

    Zhang, Zhili; Qin, Shuangjiao; Fu, Kai; Yu, Guohao; Li, Weiyi; Zhang, Xiaodong; Sun, Shichuang; Song, Liang; Li, Shuiming; Hao, Ronghui; Fan, Yaming; Sun, Qian; Pan, Gebo; Cai, Yong; Zhang, Baoshun

    2016-08-01

    We characterized an ionic liquid (1-butyl-3-methylimidazolium nitrate, C8H15N3O3) as a photo-electrochemical etchant for fabricating normally-off AlGaN/GaN metal–insulator–semiconductor high-electron-mobility transistors (MIS-HEMTs). Using the ionic liquid, we achieved an etching rate of ∼2.9 nm/min, which is sufficiently low to facilitate good etching control. The normally-off AlGaN/GaN MIS-HEMT was fabricated with an etching time of 6 min, with the 20 nm low-pressure chemical vapor deposition (LPCVD) silicon nitride (Si3N4) gate dielectric exhibiting a threshold voltage shift from ‑10 to 1.2 V, a maximum drain current of more than 426 mA/mm, and a breakdown voltage of 582 V.

  11. Synergistic effects of surfactant-assisted ionic liquid pretreatment rice straw.

    PubMed

    Chang, Ken-Lin; Chen, Xi-Mei; Han, Ye-Ju; Wang, Xiao-Qin; Potprommanee, Laddawan; Ning, Xun-An; Liu, Jing-Yong; Sun, Jian; Peng, Yen-Ping; Sun, Shui-Yu; Lin, Yuan-Chung

    2016-08-01

    The aim of this work was to study an environmentally friendly method for pretreating rice straw by using 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) as an ionic liquid (IL) assisted by surfactants. Different temperatures, reaction times, and surfactant concentrations were studied. Compared with [BMIM]Cl only pretreatment, the addition of 1% sodium dodecyl sulfate (SDS) and 1% cetyl trimethyl ammonium bromide (CTAB) increased lignin removal to 49.48% and 34.76%, respectively. Untreated and pretreated rice straw was thoroughly characterized through FTIR, XRD, and FE-SEM. Cellulose crystallinity and surface morphology of the rice straw were substantially altered after surfactant-assisted IL pretreatment. In conclusion, surfactant-assisted IL pretreatment is an effective method for producing fermentable sugars from lignocellulosic substrates. PMID:27155265

  12. Theoretical investigation of polarization effects in solution: Importance of solvent collective motions

    NASA Astrophysics Data System (ADS)

    Ishida, Tateki

    2015-01-01

    Recent theoretical studies on interesting topics related to polarization effects in solutions are presented. As one of interesting topics, ionic liquids (ILs) solvents are focused on. The collective dynamics of electronic polarizability through interionic dynamics and the effect of polarization in ILs, 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIm][PF6]), are studied with molecular dynamics simulation. Also, the time-dependent polarization effect on the probe betaine dye molecule, pyridinium N-phenoxide, in water is investigated by a time-dependent reference interaction site model self-consistent field (time-dependent RISM-SCF) approach. The importance of considering polarization effects on solution systems related to solvent collective motions is shown.

  13. Radiation stability of some room temperature ionic liquids

    NASA Astrophysics Data System (ADS)

    Jagadeeswara Rao, Ch.; Venkatesan, K. A.; Tata, B. V. R.; Nagarajan, K.; Srinivasan, T. G.; Vasudeva Rao, P. R.

    2011-05-01

    Radiation stability of some room temperature ionic liquids (RTILs) that find useful electrochemical applications in nuclear fuel cycle has been evaluated. The ionic liquids such as protonated betaine bis(trifluoromethylsulfonyl)imide (HbetNTf 2), aliquat 336 (tri-n-octlymethylammonium chloride), 1-butyl-3-methylimidazolium chloride (bmimCl), 1-hexyl-3-methylimidazolium chloride (hmimCl), N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BMPyNTf 2) and N-methyl-N-propylpiperidinium bis(trifluoromethylsulfonyl)imide (MPPiNTf 2) have been irradiated to various absorbed dose levels, up to 700 kGy. The effect of gamma radiation on these ionic liquids has been evaluated by determining the variations in the physical properties such as color, density, viscosity, refractive index and electrochemical window. The changes in density, viscosity and refractive index of these ionic liquids upon irradiation were insignificant; however, the color and electrochemical window varied significantly with increase of absorbed dose.

  14. Cellobiose as a model system to reveal cellulose dissolution mechanism in acetate-based ionic liquids: Density functional theory study substantiated by NMR spectra.

    PubMed

    Cao, Bobo; Du, Jiuyao; Du, Dongmei; Sun, Haitao; Zhu, Xiao; Fu, Hui

    2016-09-20

    Cellulose dissolution mechanism in acetate-based ionic liquids was systematically studied in Nuclear Magnetic Resonance (NMR) spectra and Density Functional Theory (DFT) methods by using cellobiose and 1-butyl-3-methylimidazolium acetate (BmimAc) as a model system. The solubility of cellulose in ionic liquid increased with temperature increase in the range of 90-140°C. NMR spectra suggested OAc(-) preferred to form stronger hydrogen bonds with hydrogen of hydroxyl in cellulose. Electrostatic potential method was employed to predict the most possible reaction sites and locate the most stable configuration. Atoms in molecules (AIM) theory was used to study the features of bonds at bond critical points and the variations of bond types. Simultaneously, noncovalent interactions were characterized and visualized by employing reduced density gradient analysis combined with Visual Molecular Dynamics (VMD) program. Natural bond orbital (NBO) theory was applied to study the noncovalent nature and characterize the orbital interactions between cellobiose and Bmim[OAc]. PMID:27261759

  15. High Performance Fe Porphyrin/Ionic Liquid Co-catalyst for Electrochemical CO2 Reduction.

    PubMed

    Choi, Jaecheol; Benedetti, Tania M; Jalili, Rouhollah; Walker, Ashley; Wallace, Gordon G; Officer, David L

    2016-09-26

    The efficient and selective catalytic reduction of CO2 is a highly promising process for both of the storage of renewable energy as well as the production of valuable chemical feedstocks. In this work, we show that the addition of an ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate, in an aprotic electrolyte containing a proton source and FeTPP, promotes the in situ formation of the [Fe(0) TPP](2-) homogeneous catalyst at a less negative potential, resulting in lower overpotentials for the CO2 reduction (670 mV) and increased kinetics of electron transfer. This co-catalysis exhibits high Faradaic efficiency for CO production (93 %) and turnover number (2 740 000 after 4 hour electrolysis), with a four-fold increase in turnover frequency (TOF) when compared with the standard system without the ionic liquid.

  16. Trivalent actinide and lanthanide separations using tetraalkyldiglycolamides (TCnDGA) in molecular and ionic liquid diluents

    SciTech Connect

    Bruce J. Mincher; Robert V. Fox; Mary E. Mincher; Chien M. Wai

    2014-09-01

    The use of the diglycolamide, tetrabutyldiglycolamide was investigated for intergroup separations of the lanthanides, focusing especially on those lanthanides (Y, Ce, Eu, Tb, Dy, Er, and Yb) found in lighting phosphors. Tetrabutyldiglycolamide extraction efficiency for the lanthanides varied depending on whether the diluent was the conventional molecular diluent 1-octanol, the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)-imide, or a mixture of the two. This was attributed to extraction of either neutral, cationic or anionic lanthanide metal complexes with nitrate ion. Based on the batch contact solvent extraction results measured here, a series of extractions providing product streams containing separated Y, Ce, Eu, Tb/Dy, and Er/Yb are proposed.

  17. Charge-Induced Long-Range Order in a Room-Temperature Ionic Liquid.

    PubMed

    Ma, Ke; Jarosova, Romana; Swain, Greg M; Blanchard, Gary J

    2016-09-20

    We report direct evidence for charge-induced long-range (ca. 100 μm) order in the room-temperature ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM(+)BF4(-)), supported on a silica surface. We have measured the rotational diffusion dynamics of anionic, cationic, and neutral chromophores as a function of distance from a silica surface. The results reflect the excess charge density gradient induced in the IL by the (negative) charge present on the silica surface. Identical measurements in ethylene glycol reveal spatially invariant reorientation dynamics for all chromophores. Capping the silica support with Me2SiCl2 results in spatially invariant reorientation dynamics in the IL. We understand these data in the context of the IL exhibiting a spatially damped piezoelectric response mediated by IL fluidity and disorder. PMID:27563803

  18. Recovery of ionic liquid via a hybrid methodology of electrodialysis with ultrafiltration after biomass pretreatment.

    PubMed

    Liang, Xiaocong; Fu, Yan; Chang, Jie

    2016-11-01

    Hybrid membrane-based methodology of electrodialysis (ED) with ultrafiltration (UF) was employed to recover the IL BmimBr (1-Butyl-3-methylimidazolium bromide) after biomass fractionation. Ultrafiltration was used to remove the residual lignin in IL solutions. Influence of molecular weight interception of UF treatment, initial IL concentration in dilute section, applied voltage and flow rate in each section of ED module were studied in detail. In this study, the highest overall IL recovery ratio reached 75.2% and the current efficiency of ED process approached 79.1%. Besides, the highest IL recovery performance of specific energy consumption was about 514.1g/kw·h. Insight gained from this study suggests a potential methodology for IL recovery after the pretreatment process for biomass. PMID:27589823

  19. Rapid carbonation for calcite from a solid-liquid-gas system with an imidazolium-based ionic liquid.

    PubMed

    Ibrahim, Abdul-Rauf; Vuningoma, Jean Bosco; Huang, Yan; Wang, Hongtao; Li, Jun

    2014-06-25

    Aqueous carbonation of Ca(OH)2 is a complex process that produces calcite with scalenohedral calcite phases and characterized by inadequate carbonate species for effective carbonation due to the poor dissolution of CO2 in water. Consequently, we report a solid-liquid-gas carbonation system with an ionic liquid (IL), 1-butyl-3-methylimidazolium bromide, in view of enhancing the reaction of CO2 with Ca(OH)2. The use of the IL increased the solubility of CO2 in the aqueous environment and enhanced the transport of the reactive species (Ca2+ and CO32-) and products. The presence of the IL also avoided the formation of the CaCO3 protective and passivation layer and ensured high carbonation yields, as well as the production of stoichiometric rhombohedral calcite phases in a short time.

  20. High Performance Fe Porphyrin/Ionic Liquid Co-catalyst for Electrochemical CO2 Reduction.

    PubMed

    Choi, Jaecheol; Benedetti, Tania M; Jalili, Rouhollah; Walker, Ashley; Wallace, Gordon G; Officer, David L

    2016-09-26

    The efficient and selective catalytic reduction of CO2 is a highly promising process for both of the storage of renewable energy as well as the production of valuable chemical feedstocks. In this work, we show that the addition of an ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate, in an aprotic electrolyte containing a proton source and FeTPP, promotes the in situ formation of the [Fe(0) TPP](2-) homogeneous catalyst at a less negative potential, resulting in lower overpotentials for the CO2 reduction (670 mV) and increased kinetics of electron transfer. This co-catalysis exhibits high Faradaic efficiency for CO production (93 %) and turnover number (2 740 000 after 4 hour electrolysis), with a four-fold increase in turnover frequency (TOF) when compared with the standard system without the ionic liquid. PMID:27464300

  1. Rapid Carbonation for Calcite from a Solid-Liquid-Gas System with an Imidazolium-Based Ionic Liquid

    PubMed Central

    Ibrahim, Abdul-Rauf; Vuningoma, Jean Bosco; Huang, Yan; Wang, Hongtao; Li, Jun

    2014-01-01

    Aqueous carbonation of Ca(OH)2 is a complex process that produces calcite with scalenohedral calcite phases and characterized by inadequate carbonate species for effective carbonation due to the poor dissolution of CO2 in water. Consequently, we report a solid-liquid-gas carbonation system with an ionic liquid (IL), 1-butyl-3-methylimidazolium bromide, in view of enhancing the reaction of CO2 with Ca(OH)2. The use of the IL increased the solubility of CO2 in the aqueous environment and enhanced the transport of the reactive species (Ca2+ and CO32−) and products. The presence of the IL also avoided the formation of the CaCO3 protective and passivation layer and ensured high carbonation yields, as well as the production of stoichiometric rhombohedral calcite phases in a short time. PMID:24968273

  2. Ionic liquid, glass or crystalline solid? Structures and thermal behaviour of (C4mim)2CuCl3.

    PubMed

    Zürner, Philipp; Schmidt, Horst; Bette, Sebastian; Wagler, Jörg; Frisch, Gero

    2016-02-28

    The ionic liquid (C4mim)2CuCl3 was synthesised from a mixture of copper(i) chloride and 1-butyl-3-methylimidazolium chloride (C4mimCl) and investigated using crystallographic and thermoanalytical methods. In the crystalline state, the compound consists of C4mim(+) cations and triangular [CuCl3](2-) anions and forms three different modifications, which are connected through phase transitions at 227 and 203 K. The high and intermediate temperature phases crystallise in the space group C2, whereas the low temperature phase exhibits the space group P21. The three crystal structures are related through an isomorphic and a klassengleiche symmetry transition, respectively. The solid undergoes congruent melting at 320 K. The enthalpy of fusion was determined to be 25.7 kJ mol(-1). The melting process is irreversible and the ionic liquid can be supercooled to its glass transition at 221 K. PMID:26785819

  3. Cellobiose as a model system to reveal cellulose dissolution mechanism in acetate-based ionic liquids: Density functional theory study substantiated by NMR spectra.

    PubMed

    Cao, Bobo; Du, Jiuyao; Du, Dongmei; Sun, Haitao; Zhu, Xiao; Fu, Hui

    2016-09-20

    Cellulose dissolution mechanism in acetate-based ionic liquids was systematically studied in Nuclear Magnetic Resonance (NMR) spectra and Density Functional Theory (DFT) methods by using cellobiose and 1-butyl-3-methylimidazolium acetate (BmimAc) as a model system. The solubility of cellulose in ionic liquid increased with temperature increase in the range of 90-140°C. NMR spectra suggested OAc(-) preferred to form stronger hydrogen bonds with hydrogen of hydroxyl in cellulose. Electrostatic potential method was employed to predict the most possible reaction sites and locate the most stable configuration. Atoms in molecules (AIM) theory was used to study the features of bonds at bond critical points and the variations of bond types. Simultaneously, noncovalent interactions were characterized and visualized by employing reduced density gradient analysis combined with Visual Molecular Dynamics (VMD) program. Natural bond orbital (NBO) theory was applied to study the noncovalent nature and characterize the orbital interactions between cellobiose and Bmim[OAc].

  4. An electrochemical fungicide pyrimethanil sensor based on carbon nanotubes/ionic-liquid construction modified electrode.

    PubMed

    Yang, Jichun; Wang, Qiong; Zhang, Minhui; Zhang, Shuming; Zhang, Lei

    2015-11-15

    In this study, a simple, rapid, sensitive and environmentally friendly electroanalytical detection method for pyrimethanil (PMT) was developed, which was based on multi-walled carbon nanotubes (MWCNTs) and ionic liquids (IL) 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]) modified glassy carbon electrode (GCE). MWCNTs-IL modified electrode significantly enhanced the oxidation peak current of PMT by combining the excellent electrochemical properties of MWCNTs and IL, suggesting that the modified electrode can remarkably improve the sensitivity of PMT detection. Under the optimum conditions, this electrochemical sensor exhibited a linear concentration range for PMT of 1.0 × 10(-7)-1.0 × 10(-4) mol L(-1) and the detection limit was 1.6 × 10(-8) mol L(-1) (S/N = 3). The fabricated electrode showed good reproducibility, stability and anti-interference, and also it was successfully employed to detect PMT in real samples.

  5. Nacre-like calcium carbonate controlled by ionic liquid/graphene oxide composite template.

    PubMed

    Yao, Chengli; Xie, Anjian; Shen, Yuhua; Zhu, Jinmiao; Li, Hongying

    2015-06-01

    Nacre-like calcium carbonate nanostructures have been mediated by an ionic liquid (IL)-graphene oxide (GO) composite template. The resultant crystals were characterized by scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectroscopy, and X-ray powder diffractometry (XRD). The results showed that either 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM]BF4) or graphene oxide can act as a soft template for calcium carbonate formation with unusual morphologies. Based on the time-dependent morphology changes of calcium carbonate particles, it is concluded that nacre-like calcium carbonate nanostructures can be formed gradually utilizing [BMIM]BF4/GO composite template. During the process of calcium carbonate formation, [BMIM]BF4 acted not only as solvents but also as morphology templates for the fabrication of calcium carbonate materials with nacre-like morphology. Based on the observations, the possible mechanisms were also discussed. PMID:25842135

  6. A study of the time-resolved fluorescence spectrum and red edge effect of ANF in a room-temperature ionic liquid.

    PubMed

    Hu, Zhonghan; Margulis, Claudio J

    2006-06-15

    In a recent article, we have analyzed using molecular dynamics simulations the steady-state red edge effect (REE) observed by Samanta and co-workers when the fluorescent probe 2-amino-7-nitrofluorene (ANF) is photoexcited at different wavelengths in 1-butyl-3-methylimidazolium ([BMIM+]) hexafluorophosphate ([PF6-]). In this letter, we predict the time- and wavelength-dependent emission spectra of ANF in the same ionic solvent. From the analysis of our simulated data, we are able to derive an approximate time scale for reorganization of the solvent around the solute probe. The effect that slow varying local liquid environments have on the overall time-dependent signal is also discussed. PMID:16771357

  7. Modified pineapple peel cellulose hydrogels embedded with sepia ink for effective removal of methylene blue.

    PubMed

    Dai, Hongjie; Huang, Huihua

    2016-09-01

    Novel composite hydrogels based on pineapple peel cellulose and sepia ink were synthesized by homogeneous acetylation of cellulose in ionic liquid 1-butyl-3-methylimidazolium chloride. The structure and morphology of the prepared hydrogels were characterized by Fourier transform infrared spectroscopy, field emission scanning electron microscope, X-ray diffraction, thermogravimetry and differential scanning calorimetry. The effects of acetylation time, acetylation temperature, molar ratio of acetic anhydride/anhydroglucose unit and the additive amount of sepia ink on methylene blue adsorption capacity of the hydrogels embedded with sepia ink were also investigated. Methylene blue adsorption of the hydrogels followed pseudo-second-order kinetic model and sepia ink improved adsorption capacity significantly. The adsorption capacity at equilibrium was increased from 53.72 to 138.25mg/g when the additive amount of sepia ink of the hydrogels was 10%. PMID:27185109

  8. Dielectric relaxation and solvation dynamics in a room-temperature ionic liquid: temperature dependence.

    PubMed

    Shim, Youngseon; Kim, Hyung J

    2013-10-01

    Dielectric relaxation, related polarization and conductivity, and solvation dynamics of the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (BMI(+)PF6(-)) are studied via molecular dynamics computer simulations in the temperature range 300 K ≤ T ≤ 500 K. Two main bands of its dielectric loss spectrum show differing temperature behaviors. As T increases, the absorption band in the microwave region shifts to higher frequencies rapidly, whereas the location of the bimodal far-IR band remains nearly unchanged. Their respective intensities tend to decrease and increase. The static dielectric constant of BMI(+)PF6(-) is found to decrease weakly with T. The ultrafast inertial component of solvation dynamics remains largely unchanged, while their dissipative relaxation component becomes faster. Roles played by ion reorientations and translations in governing dynamic and static dielectric properties of the ionic liquid are examined. A brief comparison with available experimental results is also made.

  9. Reverse dynamic calorimetry of a viscous ionic liquid.

    PubMed

    Huang, Wei; Richert, Ranko

    2009-11-14

    We compare the time scale of thermal relaxation with that of the electric modulus in the deeply supercooled regime of the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate. Thermal relaxation refers to the process of configurational temperatures of the slow degrees of freedom equilibrating toward the vibrational temperature, which is a reliable indicator for the time scale of structural relaxation. Energy is supplied to the sample by absorption from a sinusoidal electric field with amplitude as high as 387 kV/cm and frequencies in the 0.2 Hz-56 kHz range, analogous to microwave heating. The time resolved response of configurational temperature as well as the low field dielectric properties are measured in a single high field impedance setup. Near T(g), we find that the macroscopic field (or modulus M) relaxes considerably faster than the structure (in terms of thermal relaxation, solvation dynamics, and probe rotation), although the liquid is entirely composed of mobile ions.

  10. Microregion detection of ionic liquid microemulsions.

    PubMed

    Gao, Yanan; Wang, Suqing; Zheng, Liqiang; Han, Shuaibing; Zhang, Xuan; Lu, Deming; Yu, Li; Ji, Yongqiang; Zhang, Gaoyong

    2006-09-15

    Nonaqueous ionic liquid (IL) microemulsion consisting of IL, 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF(4)), surfactant TX-100, and toluene was prepared and the phase behavior of the ternary system was investigated. Electrical conductivity measurement was used for investigating the microregions of the nonaqueous IL microemulsions. On the basis of the percolation theory, the bmimBF(4)-in-toluene (IL/O), bicontinuous, and toluene-in-bmimBF(4) (O/IL) microregions of the microemulsions were successfully identified using insulative toluene as the titration phase. However, this method was invalid when conductive bmimBF(4) acted as the titration phase. The microregions obtained by conductivity measurements were further proved by electrochemical cyclic voltammetry experiments. The results indicated that the conductivity method was feasible for identifying microstructures of the nonaqueous IL microemulsions. PMID:16765365

  11. Dynamics of solvation and rotational relaxation of Coumarin 153 in ionic liquid confined nanometer-sized microemulsions.

    PubMed

    Chakrabarty, Debdeep; Seth, Debabrata; Chakraborty, Anjan; Sarkar, Nilmoni

    2005-03-31

    The effects of confinement of the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate on solvation dynamics and rotational relaxation of Coumarin 153 (C-153) in Triton X-100/cyclohexane microemulsions have been explored using steady-state and picosecond time-resolved emission spectroscopy. The steady-state and rotational relaxation data indicate that C-153 molecules are incorporated in the core of the microemulsions. The average rotational relaxation time increases with increase in w ([bmim][BF(4)]/[TX-100]) values. The solvent relaxation in the core of the microemulsion occurs on two different time scales and is almost insensitive to the increase in w values. The solvent relaxation is retarded in the pool of the microemulsions compared to the neat solvent. Though, the retardation is very small compared to several-fold retardation of the solvation time of the conventional solvent inside the pool of the microemulsions. PMID:16851624

  12. Preparation of starch nanoparticles in a water-in-ionic liquid microemulsion system and their drug loading and releasing properties.

    PubMed

    Zhou, Gang; Luo, Zhigang; Fu, Xiong

    2014-08-13

    An ionic liquid microemulsion consisting of 1-butyl-3-methylimidazolium hexafluorophosphate ([Bmim]PF₆), surfactant TX-100, 1-butanol, and water was prepared. The water-in-[Bmim]PF₆ (W/IL), bicontinuous, and [Bmim]PF₆-in-water (IL/W) microregions of the microemulsion were identified by conductivity measurements. Starch nanoparticles with a mean diameter of 91.4 nm were synthesized with epichlorohydrin as cross-linker through W/IL microemulsion cross-linking reaction at 50 °C for 4 h. Fourier transform infrared spectroscopy (FTIR) data demonstrated the formation of cross-linking bonds in starch molecules. Scanning electron microscopy (SEM) revealed that starch nanoparticles were spherical and that some particles showed aggregation formation. Furthermore, drug loading and releasing properties of starch nanoparticles were investigated with mitoxantrone hydrochloride as a drug model. This work provides an efficient and environmentally friendly approach for the preparation of starch nanoparticles, which is beneficial to their further application. PMID:25069988

  13. Plasticizing effect of ionic liquid on cellulose acetate obtained by melt processing.

    PubMed

    Bendaoud, Amine; Chalamet, Yvan

    2014-08-01

    Cellulose acetate (CA) plasticized by 1-butyl-3-methylimidazolium chloride (BMIMCl) and with diethylphtalate (DEP) was obtained by melt processing at 150°C. The effect and the interaction of ionic liquid with the cellulose acetate and their influence on structural, thermo-mechanical, rheological and tensile properties of CA materials were investigated. Ionic liquid (BMIMCl) has shown a good plasticization and more efficient destruction of the crystalline structure of cellulose acetate than the DEP plasticized CA. BMIMCl interacts intensively with CA molecules due to the pronounced van der Waals interactions, hydrogen bonding and electrostatic nature of ionic liquid. The tensile test and the low Young's modulus for plasticized CA suggest a strong reduction of the interaction between the CA chains due to the presence of the ionic liquid.

  14. Ultrasound-assisted ionic liquid-based dispersive liquid-liquid microextraction for preconcentration of patent blue V and its determination in food samples by UV-visible spectrophotometry.

    PubMed

    Unsal, Yunus Emre; Soylak, Mustafa; Tuzen, Mustafa

    2015-04-01

    Ultrasound-assisted ionic liquid-based dispersive liquid-liquid microextraction procedure (UA-IL-DLLME) was developed for determination of trace levels of patent blue V prior to its determination by UV-visible spectrophotometry. Patent blue V was extracted from 25-mL sample into a 100-μL volume of ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]), with the aid of sonication in an ultrasonic bath. Several variables affecting microextraction efficiency were optimized. Under the optimum experimental conditions, the detection limit (3 s) was 0.68 μg L(-1), and the preconcentration factor was 100. The relative standard deviation for six replicate determinations of patent blue V was 4.5%. The method was applied to the determination of patent blue V in food samples. The proposed procedure is effective, very simple, and fast.

  15. Enzymatic catalysis of formation of Z-aspartame in ionic liquid - An alternative to enzymatic catalysis in organic solvents.

    PubMed

    Erbeldinger, M; Mesiano, A J; Russell, A J

    2000-01-01

    We present the first report of enzymatic catalysis in an ionic liquid. The virtually nonexistent vapor pressure makes ionic liquids an exciting new alternative for enzyme-catalyzed syntheses in environmentally friendly environments. Z-aspartame was synthesized in a thermolysin-catalyzed reaction of carbobenzoxy-L-aspartate and L-phenylalanine methyl ester hydrochloride in 1-butyl-3-methylimidazolium hexafluorophosphate (BP6). Ionic liquids such as BP6 are thermally stable and have a remarkable range of temperatures over which they remain liquid (300 degrees C). With an initial rate of 1.2 +/- 0.1 nmol min(-)(1) mg(-)(1), we observed a competitive rate in comparison to that of enzymatic synthesis in organic solvent. Additionally, the enzyme exhibits outstanding stability, which would normally require immobilization.

  16. Efficient dehydration of 6-gingerol to 6-shogaol catalyzed by an acidic ionic liquid under ultrasound irradiation.

    PubMed

    Kou, Xingran; Li, Xingze; Rahman, Md Ramim Tanver; Yan, Minming; Huang, Huanhuan; Wang, Hongxin; Su, Yihai

    2017-01-15

    6-Gingerol and 6-shogaol are the main bioactive compounds in ginger. Although 6-shogaol has more and better bioactivities than its precursor 6-gingerol, the low content of 6-shogaol in ginger restricts its bioactive effects in functional foods. The traditional preparation methods of 6-shogaol are defective because of the environmental hazards and low efficiency of the processes. In this study, an efficient, easy and eco-friendly dehydration conversion of 6-gingerol to 6-shogaol is presented using an acidic ionic liquid 1-butyl-3-methylimidazolium hydrosulfate ([Bmim]HSO4) under ultrasound irradiation. The key parameters, including reaction temperature, reaction time, mass ratio of catalyst to substrate and ultrasonic power in each reaction process, were investigated. The yield of 6-shogaol reached as high as 97.16% under optimized condition. The catalyst could be separated from the reaction mixture and reused five times with only a slight loss of activity. PMID:27542467

  17. Crystalline characteristics of cellulose fiber and film regenerated from ionic liquid solution.

    PubMed

    Sun, Liangfeng; Chen, Jonathan Y; Jiang, Wei; Lynch, Vincent

    2015-03-15

    Regenerated cellulose fiber, fiber extrudate, and film were produced from cellulose solution prepared with raw pulp and ionic liquid solvent 1-butyl-3-methylimidazolium chloride ([BMIM]Cl). Spinning setting was based on a dry-jet and wet-spun approach including extrusion, coagulation, drawing, drying, and winding. Crystallization of the experimental fiber, fiber extrudate, and film was evaluated using a technique of wide angle X-ray diffraction (WAXD). Crystallinity index, crystallite size, and crystal orientation factor were calculated and compared among these samples. Influence of die shape, die dimension, and drawing speed on the regenerated cellulose crystallinity was discussed. The study indicated that the pulp cellulose was a Cellulose I type structure. The cellulose regeneration from the [BMIM]Cl solution completed a transformation from this intermediate phase to a final Cellulose II phase. The die shape and dimension and drawing speed were all important factors affecting the crystallinity of regenerated cellulose fiber and film. PMID:25542120

  18. Theoretical investigation of polarization effects in solution: Importance of solvent collective motions

    SciTech Connect

    Ishida, Tateki

    2015-01-22

    Recent theoretical studies on interesting topics related to polarization effects in solutions are presented. As one of interesting topics, ionic liquids (ILs) solvents are focused on. The collective dynamics of electronic polarizability through interionic dynamics and the effect of polarization in ILs, 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIm][PF{sub 6}]), are studied with molecular dynamics simulation. Also, the time-dependent polarization effect on the probe betaine dye molecule, pyridinium N-phenoxide, in water is investigated by a time-dependent reference interaction site model self-consistent field (time-dependent RISM-SCF) approach. The importance of considering polarization effects on solution systems related to solvent collective motions is shown.

  19. Molecular dynamics simulation of the behaviour of water in nano-confined ionic liquid-water mixtures.

    PubMed

    Docampo-Álvarez, B; Gómez-González, V; Montes-Campos, H; Otero-Mato, J M; Méndez-Morales, T; Cabeza, O; Gallego, L J; Lynden-Bell, R M; Ivaništšev, V B; Fedorov, M V; Varela, L M

    2016-11-23

    This work describes the behaviour of water molecules in 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid under nanoconfinement, between graphene sheets. By means of molecular dynamics simulations, the adsorption of water molecules at the graphene surface is studied. A depletion of water molecules in the vicinity of the neutral and negatively charged graphene surfaces, and their adsorption at the positively charged surface are observed in line with the preferential hydration of the ionic liquid anions. The findings are appropriately described using a two-level statistical model. The confinement effect on the structure and dynamics of the mixtures is thoroughly analyzed using the density and the potential of mean force profiles, as well as by the vibrational densities of the states of water molecules near the graphene surface. The orientation of water molecules and the water-induced structural transitions in the layer closest to the graphene surface are also discussed. PMID:27623714

  20. Electrocatalysis of CO2 Reduction in Brush Polymer Ion Gels.

    PubMed

    McNicholas, Brendon J; Blakemore, James D; Chang, Alice B; Bates, Christopher M; Kramer, Wesley W; Grubbs, Robert H; Gray, Harry B

    2016-09-01

    The electrochemical characterization of brush polymer ion gels containing embedded small-molecule redox-active species is reported. Gels comprising PS-PEO-PS triblock brush polymer, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BMIm-TFSI), and some combination of ferrocene (Fc), cobaltocenium (CoCp2(+)), and Re(bpy)(CO)3Cl (1) exhibit diffusion-controlled redox processes with diffusion coefficients approximately one-fifth of those observed in neat BMIm-TFSI. Notably, 1 dissolves homogeneously in the interpenetrating matrix domain of the ion gel and displays electrocatalytic CO2 reduction to CO in the gel. The catalytic wave exhibits a positive shift versus Fc(+/0) compared with analogous nonaqueous solvents with a reduction potential 450 mV positive of onset and 90% Faradaic efficiency for CO production. These materials provide a promising and alternative approach to immobilized electrocatalysis, creating numerous opportunities for application in solid-state devices.

  1. 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.

  2. Ionothermal synthesis process for aluminophosphate molecular sieves in the mixed water/ionic liquid system.

    PubMed

    Zhao, Zhenchao; Zhang, Weiping; Xu, Renshun; Han, Xiuwen; Tian, Zhijian; Bao, Xinhe

    2012-01-21

    The synthesis process of aluminophosphate AlPO(4)-11 molecular sieve in the mixed water/1-butyl- 3-methylimidazolium bromide ([bmim]Br) ionic liquid was investigated by XRD, multinuclear solid-state NMR, scanning electron microscopy (SEM) and X-ray energy dispersive spectroscopy (EDS). It was observed that a tablet phase, named SIZ-2, was formed at the early stage of crystallization. During crystallization metastable SIZ-2 with an incompletely condensed framework phosphorus disappeared gradually, and the phosphorous species became fully condensed through hydroxyl reaction with tetrahedral aluminum to form thermodynamically stable AlPO(4)-11 in the final product. It was found that [bmim]Br, acting as the structure-directing agent, was occluded into the AlPO(4)-11 channel.

  3. Circular dichroism studies on intermolecular interactions of amphotericin B in ionic liquid-rich environments.

    PubMed

    Jameson, Laramie P; Dzyuba, Sergei V

    2013-07-01

    Aggregation of amphotericin B (AmB) in an ionic liquid-rich environment was investigated using circular dichroism (CD) spectroscopy. It was found that nature of the ionic liquids' anion had a strong impact not only on the aggregation of AmB, but more importantly on the nature of AmB aggregates, as observed in the asymmetry of the exciton couplet of the aggregate in CD spectra. Unique CD signals for AmB aggregates were observed in three different 1-butyl-3-methylimidazolium ionic liquid solutions: [C4 -mim]Br favored the formation of AmB aggregates that were similar to those found in water, whereas [C4 -mim]BF4 and [C4 -mim]NO3 produced AmB aggregates that were different from each other and those found in water. The obtained results suggest that the designer solvent ability of ionic liquids could be expanded to address numerous intermolecular processes.

  4. Fabrication of normally-off AlGaN/GaN metal-insulator-semiconductor high-electron-mobility transistors by photo-electrochemical gate recess etching in ionic liquid

    NASA Astrophysics Data System (ADS)

    Zhang, Zhili; Qin, Shuangjiao; Fu, Kai; Yu, Guohao; Li, Weiyi; Zhang, Xiaodong; Sun, Shichuang; Song, Liang; Li, Shuiming; Hao, Ronghui; Fan, Yaming; Sun, Qian; Pan, Gebo; Cai, Yong; Zhang, Baoshun

    2016-08-01

    We characterized an ionic liquid (1-butyl-3-methylimidazolium nitrate, C8H15N3O3) as a photo-electrochemical etchant for fabricating normally-off AlGaN/GaN metal-insulator-semiconductor high-electron-mobility transistors (MIS-HEMTs). Using the ionic liquid, we achieved an etching rate of ˜2.9 nm/min, which is sufficiently low to facilitate good etching control. The normally-off AlGaN/GaN MIS-HEMT was fabricated with an etching time of 6 min, with the 20 nm low-pressure chemical vapor deposition (LPCVD) silicon nitride (Si3N4) gate dielectric exhibiting a threshold voltage shift from -10 to 1.2 V, a maximum drain current of more than 426 mA/mm, and a breakdown voltage of 582 V.

  5. 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.

  6. Advanced two-photon photolithography for patterning of transparent, electrically conductive ionic liquid-polymer nanostructures

    NASA Astrophysics Data System (ADS)

    Bakhtina, Natalia A.; MacKinnon, Neil; Korvink, Jan G.

    2016-04-01

    A key challenge in micro- and nanotechnology is the direct patterning of functional structures. For example, it is highly desirable to possess the ability to create three-dimensional (3D), conductive, and optically transparent structures. Efforts in this direction have, to date, yielded less than optimal results since the polymer composites had low optical transparency over the visible range, were only slightly conductive, or incompatible with high resolution structuring. We have previously presented the novel cross-linkable, conductive, highly transparent composite material based on a photoresist (IP-L 780, OrmoComp, or SU-8) and the ionic liquid 1-butyl-3-methylimidazolium dicyanamide. Material patterning by conventional and two-photon photolithography has been demonstrated as proof-of-concept. Aiming to increase the resolution and to extend the spectrum of exciting applications we continued our research into identifying new ionic liquid - polymer composites. In this paper, we report the precise 3D single-step structuring of optically transparent and electrically conductive ionic liquid - polymer nanostructures with the highest spatial resolution (down to 150 nm) achieved to date. This was achieved via the development of novel cross-linkable composite based on the photoresist IP-G 780 and the ionic liquid 1-butyl-3-methylimidazolium dicyanamide. The successful combination of the developed material with the advanced direct laser writing technique enabled the time- and cost-saving direct manufacturing of transparent, electrically conductive components. We believe that the excellent characteristics of the structured material will open a wider range of exciting applications.

  7. Mechanisms and rules of anion partition into ionic liquids: phenolate ions in ionic liquid/water biphasic systems.

    PubMed

    Katsuta, Shoichi; Nakamura, Ko-ichi; Kudo, Yoshihiro; Takeda, Yasuyuki

    2012-01-19

    It is important to understand the mechanisms and general rules of ion partitioning in hydrophobic ionic liquid (IL)/water biphasic systems in order to predict the extractability of an ionic species with various ILs. In this study, we have investigated the partition of picrate ion (target anion, T(-)) from aqueous sodium picrate solutions into several ILs and the accompanying changes in aqueous concentrations of the IL component cation (C(+)) and anion (A(-)) at 298.2 K. The main ILs examined are 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide, 1-butyl-3-methylimidazolium hexafluorophosphate, and 1-methyl-3-octylimidazolium bis(trifluoromethanesulfonyl)amide. The aqueous concentrations of C(+) and A(-) decreased and increased, respectively, with the extraction of T(-) into the IL phase. From the standpoint of equilibrium, the partition behavior of T(-) can be explained both by the anion exchange with A(-) in the IL phase and by the ion pair extraction with C(+) in the aqueous phase. The aqueous concentrations of C(+) and A(-) are governed by the solubility product of the IL (K(sp)). The distribution ratio of T(-) is expressed as a function of Δ[T(-)](W), namely, the difference between the initial and equilibrium concentrations of T(-) in the aqueous phase; the distribution ratio of T(-) is nearly constant when Δ[T(-)](W) < K(sp)(1/2), but decreases with increasing Δ[T(-)](W) in the larger Δ[T(-)](W) region. The equilibrium constants of the ion pair extraction and the ion exchange extraction have been determined for picrate and other phenolate ions whose partition data were previously reported. The dependences of the extraction constants and extractability on the kinds of IL component ions can be quantitatively explained on the basis of the variations of K(sp). PMID:22176301

  8. The importance of ion size and electrode curvature on electrical double layers in ionic liquids

    SciTech Connect

    Feng, G.; Qiao, R.; Huang, J; Dai, S.; Sumpter, B. G.; Meunier, V.

    2011-01-01

    Room-temperature ionic liquids (ILs) are an emerging class of electrolytes for supercapacitors. We investigate the effects of ion size and electrode curvature on the electrical double layers (EDLs) in two ILs 1-butyl-3-methylimidazolium chloride [BMIM][Cl] and 1-butyl-3-methylimidazolium hexafluorophosphate [BMIM][PF{sub 6}], using a combination of molecular dynamics (MD) and quantum density functional theory (DFT) simulations. The sizes of the counter-ion and co-ion affect the ion distribution and orientational structure of EDLs. The EDL capacitances near both planar and cylindrical electrodes were found to follow the order: [BMIM][Cl] (near the positive electrode) > [BMIM][PF{sub 6}] (near the positive electrode) ≈ [BMIM][Cl] (near the negative electrode) ≈ [BMIM][PF{sub 6}] (near the negative electrode). The EDL capacitance was also found to increase as the electrode curvature increases. These capacitance data can be fit to the Helmholtz model and the recently proposed exohedral electrical double-cylinder capacitor (xEDCC) model when the EDL thickness is properly parameterized, even though key features of the EDLs in ILs are not accounted for in these models. To remedy the shortcomings of existing models, we propose a “Multiple Ion Layers with Overscreening” (MILO) model for the EDLs in ILs that takes into account two critical features of such EDLs, i.e., alternating layering of counter-ions and co-ions and charge overscreening. The capacitance computed from the MILO model agrees well with the MD prediction. Although some input parameters of the MILO model must be obtained from MD simulations, the MILO model may provide a new framework for understanding many important aspects of EDLs in ILs (e.g., the variation of EDL capacitance with the electrode potential) that are difficult to interpret using classical EDL models and experiments.

  9. The Importance of Ion Size and Electrode Curvature on Electrical Double Layers in Ionic Liquids

    SciTech Connect

    Feng, Guang; Qiao, Rui; Huang, Jingsong; Dai, Sheng; Sumpter, Bobby G; Meunier, Vincent

    2010-01-01

    Room-temperature ionic liquids (ILs) are an emerging class of electrolytes for supercapacitors. We investigate the effects of ion size and electrode curvature on the electrical double layers (EDLs) in two ILs 1-butyl-3-methylimidazolium chloride [BMIM][Cl] and 1-butyl-3-methylimidazolium hexafluorophosphate [BMIM][PF(6)], using a combination of molecular dynamics (MD) and quantum density functional theory (DFT) simulations. The sizes of the counter-ion and co-ion affect the ion distribution and orientational structure of EDLs. The EDL capacitances near both planar and cylindrical electrodes were found to follow the order: [BMIM][Cl] (near the positive electrode) > [BMIM][PF(6)] (near the positive electrode) {approx} [BMIM][Cl] (near the negative electrode) {approx} [BMIM][PF(6)] (near the negative electrode). The EDL capacitance was also found to increase as the electrode curvature increases. These capacitance data can be fit to the Helmholtz model and the recently proposed exohedral electrical double-cylinder capacitor (xEDCC) model when the EDL thickness is properly parameterized, even though key features of the EDLs in ILs are not accounted for in these models. To remedy the shortcomings of existing models, we propose a 'Multiple Ion Layers with Overscreening' (MILO) model for the EDLs in ILs that takes into account two critical features of such EDLs, i.e., alternating layering of counter-ions and co-ions and charge overscreening. The capacitance computed from the MILO model agrees well with the MD prediction. Although some input parameters of the MILO model must be obtained from MD simulations, the MILO model may provide a new framework for understanding many important aspects of EDLs in ILs (e.g., the variation of EDL capacitance with the electrode potential) that are difficult to interpret using classical EDL models and experiments.

  10. Mechanisms and rules of anion partition into ionic liquids: phenolate ions in ionic liquid/water biphasic systems.

    PubMed

    Katsuta, Shoichi; Nakamura, Ko-ichi; Kudo, Yoshihiro; Takeda, Yasuyuki

    2012-01-19

    It is important to understand the mechanisms and general rules of ion partitioning in hydrophobic ionic liquid (IL)/water biphasic systems in order to predict the extractability of an ionic species with various ILs. In this study, we have investigated the partition of picrate ion (target anion, T(-)) from aqueous sodium picrate solutions into several ILs and the accompanying changes in aqueous concentrations of the IL component cation (C(+)) and anion (A(-)) at 298.2 K. The main ILs examined are 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide, 1-butyl-3-methylimidazolium hexafluorophosphate, and 1-methyl-3-octylimidazolium bis(trifluoromethanesulfonyl)amide. The aqueous concentrations of C(+) and A(-) decreased and increased, respectively, with the extraction of T(-) into the IL phase. From the standpoint of equilibrium, the partition behavior of T(-) can be explained both by the anion exchange with A(-) in the IL phase and by the ion pair extraction with C(+) in the aqueous phase. The aqueous concentrations of C(+) and A(-) are governed by the solubility product of the IL (K(sp)). The distribution ratio of T(-) is expressed as a function of Δ[T(-)](W), namely, the difference between the initial and equilibrium concentrations of T(-) in the aqueous phase; the distribution ratio of T(-) is nearly constant when Δ[T(-)](W) < K(sp)(1/2), but decreases with increasing Δ[T(-)](W) in the larger Δ[T(-)](W) region. The equilibrium constants of the ion pair extraction and the ion exchange extraction have been determined for picrate and other phenolate ions whose partition data were previously reported. The dependences of the extraction constants and extractability on the kinds of IL component ions can be quantitatively explained on the basis of the variations of K(sp).

  11. Ionic liquid-based microwave-assisted extraction of rutin from Chinese medicinal plants.

    PubMed

    Zeng, Huan; Wang, Yuzhi; Kong, Jinhuan; Nie, Chan; Yuan, Ya

    2010-12-15

    An ionic liquid-based microwave-assisted extraction (ILMAE) method has been developed for the effective extraction of rutin from Chinese medicinal plants including Saururus chinensis (Lour.) Bail. (S. chinensis) and Flos Sophorae. A series of 1-butyl-3-methylimidazolium ionic liquids with different anions were investigated. The results indicated that the characteristics of anions have remarkable effects on the extraction efficiency of rutin and among the investigated ionic liquids, 1-butyl-3-methylimidazolium bromide ([bmim]Br) aqueous solution was the best. In addition, the ILMAE procedures for the two kinds of medicinal herbs were also optimized by means of a series of single factor experiments and an L(9) (3(4)) orthogonal design. Compared with the optimal ionic liquid-based heating extraction (ILHE), marinated extraction (ILME), ultrasonic-assisted extraction (ILUAE), the optimized approach of ILMAE gained higher extraction efficiency which is 4.879 mg/g in S. chinensis with RSD 1.33% and 171.82 mg/g in Flos Sophorae with RSD 1.47% within the shortest extraction time. Reversed phase high performance liquid chromatography (RP-HPLC) with ultraviolet detection was employed for the analysis of rutin in Chinese medicinal plants. Under the optimum conditions, the average recoveries of rutin from S. chinensis and Flos Sophorae were 101.23% and 99.62% with RSD lower than 3%, respectively. The developed approach is linear at concentrations from 42 to 252 mg L(-1) of rutin solution, with the regression coefficient (r) at 0.99917. Moreover, the extraction mechanism of ILMAE and the microstructures and chemical structures of the two researched samples before and after extraction were also investigated. With the help of LC-MS, it was future demonstrated that the two researched herbs do contain active ingredient of rutin and ionic liquids would not influence the structure of rutin.

  12. Real-time monitoring of hydrogen peroxide consumption in an oxidation reaction in molecular solvent and ionic liquids by a hydrogen peroxide electrochemical sensor.

    PubMed

    Sordi, Daniela; Arduini, Fabiana; Conte, Valeria; Moscone, Danila; Palleschi, Giuseppe

    2011-06-20

    An efficient electrochemical protocol to monitor hydrogen peroxide consumption during metal-catalyzed oxidation by using screen-printed electrodes modified with Prussian blue is presented. In particular, cyclooctene oxidation to cyclooctene oxide, catalyzed by a vanadium(V)-salophen complex (H(2)salophen=N,N'-o-phenylenebis(salicylideneimine)), in molecular and ionic media was tested. Initially, a protocol for batch analysis was developed for a monophasic system in acetonitrile, and subsequently, an in situ protocol was developed for a biphasic system of 1-butyl-3-methylimidazolium hexafluorophosphate/phosphate buffer. Calibration curves were performed in amperometric mode by applying -50 mV versus an Ag pseudo-reference. The calibration curve of hydrogen peroxide showed a linear correlation from 1 × 10(-6) up to 5 × 10(-3) mol L(-1) with satisfactory inter- and intra-electrode reproducibility (relative standard deviation (RSD) values of 5 and 13%, respectively, for the monophasic system and 11 and 13%, respectively, for the biphasic system). Kinetic studies to investigate the oxidation reaction for both the mono- and biphasic systems have been carried out in amperometric mode as well. Firstly, the decomposition of hydrogen peroxide was examined, which showed that, in 1-butyl-3-methylimidazolium hexafluorophosphate(,) it completely decomposed in 300 min, whereas in acetonitrile, in the same time frame, 20% of the initial amount was still active. In the presence of 1% of the catalyst the decomposition rate increased in both solvents. Finally, the complete oxidation of cyclooctene was followed and the effective conversion was determined. The developed protocols showed high reproducibility, with the advantage that the environmentally friendly biphasic system could also be recycled. The good analytical performance obtained, coupled with a short analysis time, the possibility of in-line automation and the use of ionic liquids instead of molecular solvents, made this

  13. Enzymatic hydrolysis of penicillin in mixed ionic liquids/water two-phase system.

    PubMed

    Jiang, Yangyang; Xia, Hansong; Guo, Chen; Mahmood, Iram; Liu, Huizhou

    2007-01-01

    In this paper, an integrated process involving the mixed ionic liquids/water two-phase system (MILWS) is proposed to improve the efficiency for enzymatic hydrolysis of penicillin G. First, hydrophilic [C4mim]BF4 (1-butyl-3-methylimidazolium tetrafluoraborate) and NaH2PO4 salt form an ionic liquids aqueous two-phase system (ILATPS), which could extract penicillin from its fermentation broth efficiently. Second, a hydrophobic [C4mim]PF6 (1-butyl-3-methylimidazolium hexafluoraphosphate) is introduced into the ionic liquids-rich phase of ILATPS containing penicillin and converses it into MILWS. Penicillin is hydrolyzed by penicillin acylase in the water phase of MILWS at pH 5. The byproduct phenylacetic acid (PAA) is partitioned into the ionic liquids mixture phase, while the intended product 6-aminopenicillanic acid (6-APA) is precipitated at this pH. In comparison with a similar butyl acetate/water system (BAWS) at pH 4, MILWS exhibits two advantages. (1) The selectivity between PAA and penicillin is greatly optimized at pH 5 by varying the mole ratio of [C4mim]PF6/[C4mim]BF4 in MILWS, whereas in BAWS the unalterable nature of the organic solvent restricts the optimized pH for maximum selectivity between PAA and penicillin at pH 4. (2) The pH for 6-APA precipitation in BAWS is 4, whereas it shifts to pH 5 in MILWS due to the complexation between negatively charged 6-APA and the cationic surface of the ionic liquids micelle. As a result, the removal of the two products from the enzyme sphere at relatively high pH is permitted in MILWS, which is beneficial for enzymatic activity and stability in comparison with the acidic pH 4 environment in BAWS.

  14. Evaluation of thermophysical properties of ionic liquids with polar solvent: a comparable study of two families of ionic liquids with various ions.

    PubMed

    Govinda, Varadhi; Attri, Pankaj; Venkatesu, Punnuru; Venkateswarlu, Ponneri

    2013-10-17

    In this work, we explore and compare the role of the ion effect on the thermophysical properties of two families of ionic liquids (ILs), namely, tetra-alkyl ammonium cation [R4N](+) with hydroxide [OH](-) anion and 1-alkyl-3-methyl imidazolium cation [amim](+) with different anions (chloride, methyl sulfate, and tetrafluoroborate), with polar solvent such as dimethylsulfoxide (DMSO) in the temperature range from 25 to 40 °C and over the whole concentration range of ILs. Two families of ILs, namely, tetramethyl ammonium hydroxide [(CH3)4N][OH] (TMAH), tetraethyl ammonium hydroxide [(C2H5)4N][OH] (TEAH), tetrapropyl ammonium hydroxide [(C3H7)4N][OH] (TPAH), and tetrabutyl ammonium hydroxide [(C4H9)4N][OH] (TBAH) from ammonium-based ILs and 1-ethyl-3-methylimidazolium chloride [Emim][Cl], 1-ethyl-3-methylimidazolium methylsulfate [Emim][MeSO4], 1-butyl-3-methylimidazolium tetrafluoroborate [Bmim][BF4], and 1-butyl-3-methylimidazolium chloride ([Bmim][Cl]) from imidazolium family of ILs, are used in the present study. To address the molecular interactions of ILs with DMSO, densities (ρ), ultrasonic sound velocities (u), and viscosities (η) have been measured over the entire composition range and at four temperatures, 25, 30, 35, and 40 °C, under atmospheric pressure. From these experimental data, the excess molar volume (V(E)), the deviation in isentropic compressibility (Δκs), and the deviation in viscosity (Δη) were calculated and were adequately correlated by using the Redlich-Kister polynomial equation. The measured and predicted data were interpreted on the basis of intermolecular interactions and structural effects between like and unlike molecules upon mixing. The hydrogen-bonding features between ammonium-based ILs and DMSO were analyzed using molecular modeling program by HyperChem 7. PMID:24087984

  15. Synthesis and characterization of ionomers as polymer electrolytes for energy conversion devices

    NASA Astrophysics Data System (ADS)

    Oh, Hyukkeun

    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

  16. Computational and experimental study of the interactions between ionic liquids and volatile organic compounds.

    PubMed

    Gao, Tingting; Andino, Jean M; Alvarez-Idaboy, J Raul

    2010-09-01

    Computational chemistry calculations were performed to investigate the interactions of ionic liquids with different classes of volatile organic compounds (VOCs), including alcohols, aldehydes, ketones, alkanes, alkenes, alkynes and aromatic compounds. At least one VOC was studied to represent each class. Initially, 1-butyl-3-methylimindazolium chloride (abbreviated as C(4)mimCl) was used as the test ionic liquid compound. Calculated interaction lengths between atoms in the ionic liquid and the VOC tested as well as thermodynamic data suggest that C(4)mimCl preferentially interacts with alcohols as compared to other classes of volatile organic compounds. The interactions of methanol with different kinds of ionic liquids, specifically 1-butyl-3-methylimidazolium bromine (C(4)mimBr) and 1-butyl-3-methylimidazolium tetrafluoroborate (C(4)mimBF(4)) were also studied. In comparing C(4)mimCl, C(4)mimBr, and C(4)mimBF(4), the computational results suggest that C(4)mimCl is more likely to interact with methanol. Laboratory experiments were performed to provide further evidence for the interaction between C(4)mimCl and different classes of VOCs. Fourier transform infrared spectroscopy was used to probe the ionic liquid surface before and after exposure to the VOCs that were tested. New spectral features were detected after exposure of C(4)mimCl to various alcohols. The new features are characteristic of the alcohols tested. No new IR features were detected after exposure of the C(4)mimCl to the aldehyde, ketone, alkane, alkene, alkyne or aromatic compounds studied. In addition, after exposing the C(4)mimCl to a multi-component mixture of various classes of compounds (including an alcohol), the only new peaks that were detected were characteristic of the alcohol that was tested. These experimental results demonstrated that C(4)mimCl is selective to alcohols, even in complex mixtures. The findings in this work provide information for future gas-phase alcohol sensor design

  17. The Barium Hydroxide-Ammonium Thiocyanate Reaction: A Titrimetric Continuous Variations Experiment.

    ERIC Educational Resources Information Center

    Harris, Arlo D.

    1979-01-01

    Presents an experiment for inorganic, organic, or physical chemistry students utilizing acid-base titrimetry to study the stoichiometric of a solid state reaction. Time involved ranges from one to three, three-hour lab periods. (Author/SA)

  18. Determination of Free Acid by Standard Addition with Potassium Thiocyanate as Complexant

    SciTech Connect

    Baumann, E.W.

    2001-05-29

    A method is described for determination of free acid in solutions containing the hydrolyzable ions Al (III), Cr(III), Fe(III), Hg(II), Ni(II), Th(IV), and U(VI). The concentration of the sample is calculated either by solving three simultaneous Nernst equations, by the Gran plot procedure, or by means of a microprocessor pH meter. Molar concentrations of metal ion up to 2.5 times that of the acid can be tolerated. The method has been applied to analysis of nuclear processing solutions that contain Pu(III), in addition to the ions listed above.

  19. New thiocyanate potentiometric sensors based on sulfadimidine metal complexes: experimental and theoretical studies.

    PubMed

    Shehab, Ola R; Mansour, Ahmed M

    2014-07-15

    Three sulfadimidine metal complexes (M=Fe(III), Cu(II), and Ag(I)) were prepared, characterized, and examined as neutral carriers for the determination of SCN(-) using modified carbon paste electrode. These sensors were successfully applied in the pure samples, and biological fluids. The electrode mechanism was investigated by UV-vis and FT IR. The experimental studies were complemented by quantum chemical calculations at DFT/B3LYP level of theory. The best performance was observed for Cu(II) electrode (C) containing 7.0% complex, 53.0% o-nitrophenyloctyl ether, 37.0% graphite and 3.0% cetylpyridinium chloride, and also for Fe(III)-electrode (A) having 6.0% complex, 52.0% o-nitro phenyloctyl ether, 40.5% graphite and 2.5% cetylpyridinium chloride.

  20. Removal of phenols, thiocyanate and ammonium from coal gasification wastewater using moving bed biofilm reactor.

    PubMed

    Li, Hui-qiang; Han, Hong-jun; Du, Mao-an; Wang, Wei

    2011-04-01

    A laboratory-scale moving bed biofilm reactor (MBBR) with a volume of 4 L was used to study the biodegradation of coal gasification wastewater. Maximum removal efficiencies of 81%, 89%, 94% and 93% were obtained for COD, phenols, SCN(-) and NH(4)(+)-N, respectively. NO(2)(-)-N accumulation induced increase of effluent COD concentration when the hydraulic residence time (HRT) decreased. Phenols removal was not affected when the HRT decreased from 48 to 32 h. Effluent SCN(-) and NH(4)(+)-N concentration increased with the decrease of the HRT, and decreased gradually when the HRT returned to 48 h. Batch experiments were carried out to study performance of the suspended and attached growth biomass in the MBBR.

  1. Three dimensional ink-jet printing of biomaterials using ionic liquids and co-solvents.

    PubMed

    Gunasekera, Deshani H A T; Kuek, SzeLee; Hasanaj, Denis; He, Yinfeng; Tuck, Christopher; Croft, Anna K; Wildman, Ricky D

    2016-08-15

    1-Ethyl-3-methylimidazolium acetate ([C2C1Im][OAc]) and 1-butyl-3-methylimidazolium acetate ([C4C1Im][OAc]) have been used as solvents for the dissolution and ink-jet printing of cellulose from 1.0 to 4.8 wt%, mixed with the co-solvents 1-butanol and DMSO. 1-Butanol and DMSO were used as rheological modifiers to ensure consistent printing, with DMSO in the range of 41-47 wt% producing samples within the printable range of a DIMATIX print-head used (printability parameter < 10) at 55 °C, whilst maintaining cellulose solubility. Regeneration of cellulose from printed samples using water was demonstrated, with the resulting structural changes to the cellulose sample assessed by scanning electron microscopy (SEM) and white light interferometry (WLI). These results indicate the potential of biorenewable materials to be used in the 3D additive manufacture process to generate single-component and composite materials. PMID:27231729

  2. Choline chloride-thiourea, a deep eutectic solvent for the production of chitin nanofibers.

    PubMed

    Mukesh, Chandrakant; Mondal, Dibyendu; Sharma, Mukesh; Prasad, Kamalesh

    2014-03-15

    Deep eutectic solvents (DESs) consisting of the mixtures of choline halide (chloride/bromide)-urea and choline chloride-thiourea were used as solvents to prepare α-chitin nanofibers (CNFs). CNFs of diameter 20-30 nm could be obtained using the DESs comprising of the mixture of choline chloride and thiourea (CCT 1:2); however, NFs could not be obtained using the DESs having urea (CCU 1:2) as hydrogen bond donor. The physicochemical properties of thus obtained NFs were compared with those obtained using a couple of imidazolium based ionic liquids namely, 1-butyl-3-methylimidazolium hydrogen sulphate [(Bmim)HSO4] and 1-methylimidazolium hydrogen sulphate [(Hmim)HSO4] as well as choline based bio-ILs namely, choline hydrogen sulphate [(Chol)HSO4] and choline acrylate. The CNFs obtained using the DES as a solvent were used to prepare calcium alginate bio-nanocomposite gel beads having enhanced elasticity in comparison to Ca-alginate beads. The bio-nanocomposite gel beads thus obtained were used to study slow release of 5-fluorouracil, an anticancer drug. PMID:24528755

  3. Novel applications of ionic liquids in materials processing

    NASA Astrophysics Data System (ADS)

    Reddy, Ramana G.

    2009-05-01

    Ionic liquids are mixtures of organic and inorganic salts which are liquids at room temperature. Several potential applications of ionic liquids in the field of materials processing are electrowinning and electrodeposition of metals and alloys, electrolysis of active metals at low temperature, liquid-liquid extraction of metals. Results using 1-butyl-3-methylimidazolium chloride with AlCl3 at low temperatures yielded high purity aluminium deposits (>99.9% pure) and current efficiencies >98%. Titanium and aluminium were co-deposited with/without the addition of TiCl4 with up to 27 wt% Ti in the deposit with current efficiencies in the range of 78-85 %. Certain ionic liquids are potential replacements for thermal oils and molten salts as heat transfer fluids in solar energy applications due to high thermal stability, very low corrosivity and substantial sensible heat retentivity. The calculated storage densities for several chloride and fluoride ionic liquids are in the range of 160-210 MJ/m3. A 3-D mathematical model was developed to simulate the large scale electrowinning of aluminium. Since ionic liquids processing results in their low energy consumption, low pollutant emissions many more materials processing applications are expected in future.

  4. Sodium bromide induced micelle to vesicle transitions of newly synthesized anionic surface active ionic liquids based on dodecylbenzenesulfonate.

    PubMed

    Rao, K Srinivasa; Gehlot, Praveen Singh; Gupta, Hariom; Drechsler, Markus; Kumar, Arvind

    2015-03-19

    Dodecylbenezenesulfonate-based anionic surface active ionic liquids (DBS-ILs) paired with onium cations, n-butyltrimethylammonium ([N1114]), 1-butyl-3-methylimidazolium ([C4mim]), and N-butylpyridinium ([C4Py]) have been synthesized. DBS-ILs were found to be highly surface active having critical micelle concentration (CMC) lower than that of their conventional analogue sodium dodecylbenezenesulfonate ([Na][DBS]). The CMC values of DBS-ILs were determined from surface tension (ST) and isothermal titration calorimetry (ITC). DBS-ILs formed micelles predominantly in the aqueous medium, and unlike [Na]DBS, the micelles of DBS-ILs could be transformed into vesicles with the addition of sodium bromide (NaBr). Micelle to vesicle transitions (MVTs) were evidenced from dynamic light scattering (DLS), turbidity, proton nuclear magnetic resonance ((1)H NMR), and cryo-TEM techniques. Thermodynamics of aggregation was investigated from ITC which indicated that the aggregation process is primarily driven by the entropy factor. The formation of a vesicle upon addition of NaBr has been accounted to the increased electrostatic interactions between the less hydrated sulfonate headgroup and the more populated bigger sized counterions along with the favored cation-π or π-π interactions between them as evidenced from 2D-NOESY NMR experiments. The stimuli-responsive morphological transitions in the self-assembly of the reported anionic surface active ionic liquids (SAILs) will be useful for encapsulation and delivery of active (bio)molecules in the targeted biomedical applications.

  5. Gels and lyotropic liquid crystals: using an imidazolium-based catanionic surfactant in binary solvents.

    PubMed

    Cheng, Ni; Hu, Qiongzheng; Bi, Yanhui; Xu, Wenwen; Gong, Yanjun; Yu, Li

    2014-08-01

    The self-assembly behavior of an imidazolium-based catanionic surfactant, 1-butyl-3-methylimidazolium dodecylsulfate ([C4mim][C12H25SO4]), was investigated in water-ethylammonium nitrate (EAN) mixed solvents with different volume ratios. It is particular interesting that this simple surfactant could not only form lyotropic liquid crystals (LLC) with multimesophases, i.e., normal hexagonal (H1), lamellar liquid crystal (Lα), and reverse bicontinuous cubic phase (V2), in the water-rich environment but also act as an efficient low-molecular-weight gelator (LMWG) which gelated EAN-abundant binary media in a broad concentration range. The peculiar nanodisk cluster morphology of gels composed of similar bilayer units was first observed. FT-IR spectra and density functional theory (DFT) calculations reveal that strong H bonding and electrostatic interactions between EAN and the headgroups of [C4mim][C12H25SO4] are primarily responsible for gelation. The self-assembled gels displayed excellent mechanical strength and a thermoreversible sol-gel transition. It is for the first time that a rich variety of controllable ordered aggregates could be observed only by simply modulating the concentration of a single imidazolium-based catanionic surfactant or the ratio of mixed solvents. This environmentally friendly system is expected to have broad applications in various fields, such as materials science, drug delivery systems, and supramolecular chemistry.

  6. Bucky-gel coated glassy carbon electrodes, for voltammetric detection of femtomolar leveled lead ions.

    PubMed

    Wan, Qijin; Yu, Fen; Zhu, Lina; Wang, Xiaoxia; Yang, Nianjun

    2010-10-15

    Femtomolar (fM) leveled lead ions were electrochemically detected using a bucky-gel coated glassy carbon electrode and differential pulse anodic stripping voltammetry. The bucky-gel was composed of dithizone, ionic liquid (1-butyl-3-methylimidazolium hexafluorophosphate), and multi-walled carbon nanotubes (MWCNTs). The fabrication of the bucky-gel coated electrode was optimized. The modified electrode was characterized with voltammetry, electrochemical impedance spectroscopy, and chronoamperometry. After the accumulation of lead ions into the bucky-gel modified electrode at -1.2V vs. saturated calomel electrode (SCE) for 5 min in a pH 4.4 sodium acetate-acetate acid buffer solution, differential pulse anodic stripping voltammograms of the accumulated lead show an anodic wave at -0.58 V. The anodic peak current is detectable for lead ions in the concentration range from 1.0 μM down to 500 fM. The detection limit is calculated to be 100 fM. The proposed method was successfully applied for the detection of lead ions in lake water. PMID:20875583

  7. Synthesis of Cu, Zn and Cu/Zn brass alloy nanoparticles from metal amidinate precursors in ionic liquids or propylene carbonate with relevance to methanol synthesis.

    PubMed

    Schütte, Kai; Meyer, Hajo; Gemel, Christian; Barthel, Juri; Fischer, Roland A; Janiak, Christoph

    2014-03-21

    Microwave-induced decomposition of the transition metal amidinates {[Me(C(N(i)Pr)2)]Cu}2 (1) and [Me(C(N(i)Pr)2)]2Zn (2) in the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF4]) or in propylene carbonate (PC) gives copper and zinc nanoparticles which are stable in the absence of capping ligands (surfactants) for more than six weeks. Co-decomposition of 1 and 2 yields the intermetallic nano-brass phases β-CuZn and γ-Cu3Zn depending on the chosen molar ratios of the precursors. Nanoparticles were characterized by high-angle annular dark field-scanning transmission electron microscopy (HAADF-STEM), dynamic light scattering and powder X-ray diffractometry. Microstructure characterizations were complemented by STEM with spatially resolved energy-dispersive X-ray spectrometry and X-ray photoelectron spectroscopy. Synthesis in ILs yields significantly smaller nanoparticles than in PC. β-CuZn alloy nanoparticles are precursors to catalysts for methanol synthesis from the synthesis gas H2/CO/CO2 with a productivity of 10.7 mol(MeOH) (kg(Cu) h)(-1).

  8. A striking effect of ionic-liquid anions in the extraction of Sr2+ and Cs+ by dicyclohexano-18-crown-6

    SciTech Connect

    Luo, Huimin; Dai, Sheng; Bonnesen, Peter V; Haverlock, Tamara; Moyer, Bruce A; Buchanan III, A C

    2006-01-01

    The nature of the ionic-liquid (IL) anion has been found to have a remarkable effect on the solvent extraction of Sr2+ and Cs+ by dicyclohexano-18-crown-6 dissolved in ionic liquids. In particular, the extraction efficiency increases with the hydrophobicity of the IL anion as reflected by the solubility in water of ILs having a common cation. Since a cation-exchange mechanism is operating in these systems, the influence of the IL anion is in large part attributable to an expected Le Chatelier effect in which a greater aqueous concentration of IL cation, obtained when using an IL anion of lower hydrophobicity, opposes cation exchange. This dependence is opposite to that found for IL cations, indicating a significant advantage of using ILs with hydrophobic anions for cation extraction. Furthermore, the extraction selectivity for Sr2+ over Na+, K+, and Cs+ can be significantly improved through the use of hydrophobic anions for the ILs containing 1-ethyl-3-methylimidazolium or 1-butyl-3-methylimidazolium cations.

  9. Understanding positive and negative deviations in polarity of ionic liquid mixtures by pseudo-solvent approach.

    PubMed

    Beniwal, Vijay; Kumar, Anil

    2016-08-24

    Physico-chemical properties of liquid mixtures in general display large deviations from linear behaviour, arising out of complex specific and non-specific intermolecular interactions. The polarity of liquid mixtures displaying large positive and negative deviations can be minimized and linear mixing can be achieved in liquids using a pseudo-solvent methodology. The work described herein is designed to investigate the influence of different physical parameters on the linear pseudo-solvent composition in ionic liquid mixtures. For this purpose, we have determined the deviations from linearity, ΔE values (defined as given by ) for binary mixtures of a variety of ionic liquids, including two molecular solvents, DMSO and formamide. Firstly, the investigations were carried out in three 1-butyl-3-methylimidazolium cation based aprotic ionic liquids and the roles of anionic structure and hydrogen bond acceptor basicities (β values) of the ionic liquids were determined. The influence of the cationic structure, i.e., the hydrogen bond donor acidity (α values) and non-associative nature of the ionic liquids, was determined using C2-methylated analogs, 1-butyl-2,3-dimethylimidazolium cation based ionic liquids. The role of the protic nature of ionic liquids was studied in two protic ionic liquids, viz., 1-methylimidazolium formate and 1-methylimidazolium acetate. The effects of the temperature, pseudo-solvent structure and solvatochromic probe structure on the ΔE values were also explored.

  10. Role of LiBF4 in Ionic Liquid Membranes for Facilitated CO2 Transport.

    PubMed

    Choi, Yeji; Hong, Gil Hwan; Kang, Sang Wook

    2016-03-01

    The ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM BF4)/LiBF4 electrolyte was prepared for highly selective facilitated CO2 transport membranes. When LiBF4 was incorporated into BMIM BF4, synergy effects by free Li+ ion and imidazolium cations is expected to enhance the separation performance for CO2/N2 and CO2/CH4. The free state of BF4- ions in BMIM BF4/LiBF4 solutions was investigated by FT-Raman spectroscopy. For the coordination of LiBF4 with BMIMBF4, thermal gravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS) was utilized. Electrolyte membranes consisting of BMIM BF4 and LiBF4 showed selectivities of 8.40 and 8.25 for CO2/N2 and CO2/CH4, respectively. Neat BMIM BF4 membrane showed selectivities of 5.0 and 4.8, respectively. Enhanced separation performance was attributed to increased free Li+ and abundant free imidazolium cations. PMID:27455716

  11. Comparative ecotoxicology study of two neoteric solvents: Imidazolium ionic liquid vs. glycerol derivative.

    PubMed

    Perales, Eduardo; García, Cristina Belén; Lomba, Laura; Aldea, Luis; García, José Ignacio; Giner, Beatriz

    2016-10-01

    In this study we have compared the acute ecotoxicity of two solvents, with very different structure and origin, but sharing many physical-chemical properties, so they can be used for similar purposes; a well-known ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]) and a solvent partially derived from biomass, 3-bis(2,2,2-trifluoroethoxy)propan-2-ol (BTFIP). We have used three biomodels (Vibrio fischeri, Daphnia magna and Danio rerio) and performed the comparison applying the Environmental, Health and Safety (EHS) hazard assessment. According to the results, ecotoxicity of [BMIM][PF6] and BTFIP is quite similar in the simplest model Vibrio fischeri, while in Daphnia magna [BMIM][PF6] is clearly more toxic. However, in Danio rerio, toxicity of these chemicals is again quite similar and both can be classified as "nontoxic". The higher index value of [BMIM][PF6] in water mediate effect in the EHS assessment indicates that this ionic liquid is more dangerous than BTFIP, although accumulation and degradation properties have not been taken into account. Further studies will be necessary to ascertain these conclusions.

  12. Hydrolysis of microcrystalline cellulose using functionalized Bronsted acidic ionic liquids - A comparative study.

    PubMed

    Parveen, Firdaus; Patra, Tanmoy; Upadhyayula, Sreedevi

    2016-01-01

    Cellulose conversion to platform chemicals is required to meet the demands of increasing population and modernization of the world. Hydrolysis of microcrystalline cellulose was studied with SO3H, COOH and OH functionalized imidazole based ionic liquid using 1-butyl-3-methylimidazolium chloride [BMIM]Cl as a solvent. The influence of temperature, time, acidity of ionic liquids and catalyst loading was studied on hydrolysis reaction. The maximum %TRS yield 85%, was obtained at 100°C and 90min with 0.2g of SO3H functionalized ionic liquid. UV-vis spectroscopy using 4-nitro aniline as an indicator was performed to find out the Hammett function of ionic liquid and acidity trends are as follows: SO3H>COOH>OH. Density functional theory (DFT) calculations were performed to optimize the ionic liquid and their conjugate bases at B3LYP 6-311G++ (d, p) level using Gaussian 09 program. Theoretical findings are in agreement with the experimental results.

  13. Monolithic column incorporated with lanthanide metal-organic framework for capillary electrochromatography.

    PubMed

    Zhang, Li-Shun; Du, Pei-Yao; Gu, Wen; Zhao, Qing-Li; Huang, Yan-Ping; Liu, Zhao-Sheng

    2016-08-26

    A new lanthanide metal-organic frameworks NKU-1 have successfully incorporated into poly (BMA-co-EDMA) monolith and evaluated by capillary electrochromatography (CEC). Lanthanide metal-organic frameworks [Eu2(ABTC)1.5(H2O)3(DMA)] (NKU-1) were synthesized by self-assembly of Eu(III) ions and 3,3',5,5'-azo benzene tetracarboxylic acid ligands have been fabricated into poly(BMA-co-EDMA) monoliths. 1-Butyl-3-methylimidazolium tetrafluoroborate and N,N-dimethylformamide were developed as binary porogen obtaining homogeneous dispersibility for NKU-1 and high permeability for monolithic column. The successful incorporation of NKU-1 into poly(BMA-co-EDMA) was confirmed and characterized by FT-IR spectra, scanning electron microscopy, X-ray diffraction, energy dispersive spectrometer area scanning, and transmission electron microscopy. Separation ability of the NKU-1-poly (BMA-co-EDMA) monoliths was demonstrated by separating four groups of analytes in CEC, including alkylbenzenes, polycyclic aromatic hydrocarbon, aniline series and naphthyl substitutes. Compared with bare monolithic (column efficiency of 100,000plates/m), the NKU-1-poly (BMA-co-EDMA) monoliths have displayed greater column efficiency (maximum 210,000plates/m) and higher permeability, as well as less peak tailing. The results showed that the NKU-1-poly (BMA-co-EDMA) monoliths are promising stationary phases for CEC separations. PMID:27432788

  14. Green synthesis of polymer monoliths incorporated with carbon nanotubes in room temperature ionic liquid and deep eutectic solvents.

    PubMed

    Zhang, Li-Shun; Gao, Shu-Ping; Huang, Yan-Ping; Liu, Zhao-Sheng

    2016-07-01

    In this work, an efficient method to prepare polymer monoliths with incorporated carbon nanotubes in a mixture of room temperature ionic liquid and deep eutectic solvents was developed. With assistance of the binary green solvent, 1-butyl-3-methylimidazolium tetrafluoroborate and choline chloride/ethylene glycol, single-walled carbon nanotubes were dispersed successfully in pre-polymerization mixture without need of oxidative cutting of carbon nanotubes, which may allow depletion of the emission of volatile organic compounds into environment. The novel single-walled carbon nanotubes monolith was evaluated by capillary electrochromatography. Compared with the monolith made without single-walled carbon nanotubes, the monolith with the incorporation of single-walled carbon nanotubes exhibited high column efficiency (251,000plates/m) in the chromatographic separation. The morphology of the monolith can be tuned by the composition of mixture of ionic liquids and deep eutectic solvents to afford good column permeability and excellent separation ability for small molecules of alkyl phenones and alkyl benzenes. The results demonstrated that the method is a green strategy for the fabrication of multifunctional polymer monoliths. PMID:27154683

  15. Effects of Water on Solvation Layers of Imidazolium-Type Room Temperature Ionic Liquids on Silica and Mica.

    PubMed

    Sakai, Kenichi; Okada, Kohei; Uka, Akihito; Misono, Takeshi; Endo, Takeshi; Sasaki, Shinya; Abe, Masahiko; Sakai, Hideki

    2015-06-01

    Effects of the addition of water on solvation layers of imidazolium-type room temperature ionic liquids (RT-ILs) have been studied through force curve measurements of atomic force microscopy (AFM). Two kinds of RT-ILs were employed in this study; one is a hydrophilic RT-IL (1-butyl-3-methylimidazolium tetrafluoroborate, BmimBF4), and the other is a hydrophobic one (1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, EmimTFSI). These RT-ILs form solvation layers on hydrophilic solid substances (i.e., silica and mica) in the absence of added water. The addition of water into BmimBF4 resulted in the disruption of the solvation layers and then the formation of an interfacial water phase on silica. In contrast, the formation of the interfacial water phase was not evidenced on mica because of the absence of hydrogen-bonding sites on the mica surface. Interestingly, the addition of water into EmimTFSI induced the formation of the interfacial water phase on the two solid surfaces. In the EmimTFSI system, importantly, significantly greater adhesion forces were observed on silica than on mica. This reflects the different formation mechanisms of the interfacial water phase on the two solid surfaces. We conclude that the hydrogen bonding is a key factor in determining whether water molecules can be adsorbed on the solid surfaces, but it is also necessary to take into account the hydrophilic/hydrophobic nature of the RT-ILs.

  16. Comparing an ionic liquid to a molecular solvent in the cesium cation extraction by a calixarene: a molecular dynamics study of the aqueous interfaces.

    PubMed

    Sieffert, Nicolas; Wipff, Georges

    2006-10-01

    We report a molecular dynamics (MD) study of the interfacial behavior of key partners involved in the Cs(+) cation extraction by a calix[4]arene-crown-6 host (L), comparing an ionic liquid (IL) to a classical molecular solvent (chloroform) as receiving "oil" phase. The IL is composed of hydrophobic 1-butyl-3-methylimidazolium cations (BMI(+)) and bis(trifluoromethylsulfonyl)imide anions (Tf(2)N(-)) and forms a biphasic system with water. The simulations reveal similarities but also interesting differences between the two types of interfaces. Much longer times are needed to "equilibrate" IL systems, compared to classical liquid mixtures, and there is more intersolvent mixing with the IL than with chloroform, especially concerning the water-in-oil content. There is also some excess of the BMI(+) cations over the Tf(2)N(-) anions in the aqueous phase. Simulations on the Na(+)NO(3)(-) and Cs(+)NO(3)(-) ions show that they sometimes interact at the interface with the IL ions, forming hydrated intimate ion pairs, whereas they are "repelled" by the classical interface. The LCs(+) complex and L ligand also behave differently, depending on the "oil phase". They are better solvated by the IL than by chloroform and thus poorly attracted at the IL interface, whereas they adsorb at the chloroform interface, adopting well-defined amphiphilic orientations. The results are discussed in the context of assisted ion transfer and provide a number of arguments explaining the specificity and efficiency of IL based, compared to classical extraction systems.

  17. Multi-podant diglycolamides and room temperature ionic liquid impregnated resins: An excellent combination for extraction chromatography of actinides.

    PubMed

    Gujar, R B; Ansari, S A; Verboom, W; Mohapatra, P K

    2016-05-27

    Extraction chromatography resins, prepared by impregnating two multi-podant diglycolamide ligands, viz. diglycolamide-functionalized calix[4]arene (C4DGA) and tripodal diglycolamide (T-DGA) dissolved in the room temperature ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide (RTIL: C4mimTf2N) on Chromosorb-W (an inert solid support), gave excellent results for the removal of trivalent actinides from acidic waste solutions. Distribution coefficient measurements on several metal ions showed selective sorption of Am(III) over hexavalent uranyl ions and other fission product elements such as strontium and cesium. The sorbed metal ions could be efficiently desorbed with a complexing solution containing guanidine carbonate and EDTA buffer. The sorption of Am(III) on both resins followed pseudo-second order rate kinetics with rate constants of 1.37×10(-6) and 6.88×10(-7)g/cpmmin for T-DGA and C4DGA resins, respectively. The metal sorption on both resins indicated the Langmuir monolayer chemisorption phenomenon with Eu(III) sorption capacities of 4.83±0.21 and 0.52±0.05mg per g of T-DGA and C4DGA resins, respectively. The results of column studies show that these resins are of interest for a possible application for the recovery of hazardous trivalent actinides from dilute aqueous solutions. PMID:27130582

  18. [Separation and determination of optical isomers of phenylephrine by chiral ligand exchange capillary elcctrophoresis coupling with the promoting effect of ionic liquid].

    PubMed

    Yang, Simei; Zhang, Jiayao; Li, Fei; Hu, Xufang; Cao, Qiue

    2016-01-01

    A method for the separation and determination of optical isomers of phenylephrine was developed based on the promoting effect of non-chiral ionic liquid on chiral ligand-exchange capillary electrophoresis after the electrophoretic parameters were optimized systematically. R-phenylephrine and S-phenylephrine can be separated and determined effectively in 20 mmol/L Tris-H3PO4 buffer solution (pH 5.4) composed of 4.0 mmol/L Cu(II), 8.0 mmol/L L-proline (L-Pro) and 15 mmol/L 1-butyl-3-methylimidazolium chloride ([BMIM] Cl) with the applied voltage of 20 kV, capillary temperature of 25 °C , detection wavelength of 254 nm, and injection of 5 s at 3,447 Pa. The resolution of R- and S-phenylephrines was 1. 42. The linear ranges for the determination of R-phenylephrine and S-phenylephrine were 12. 5 - 150 mg/L and 15. 0-150 mg/L, respectively. The method has been satisfactorily used for the determination of R-phenylephrine and S-phenylephrine in the spiked blood and urine samples. The spiked recoveries in the urine sample were in the range of 93. 7% -108. 2% with the RSDs lower than 3. 18% (n= 3) , and the spiked recoveries in the blood sample were in the range of 91. 4% and 113. 1% with the RSDs lower than 4. 82% (n =3).

  19. Thermostable gel polymer electrolyte based on succinonitrile and ionic liquid for high-performance solid-state supercapacitors

    NASA Astrophysics Data System (ADS)

    Pandey, Gaind P.; Liu, Tao; Hancock, Cody; Li, Yonghui; Sun, Xiuzhi Susan; Li, Jun

    2016-10-01

    A flexible, free-standing, thermostable gel polymer electrolyte based on plastic crystalline succinonitrile (SN) and ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate (BMImBF4) entrapped in copolymer poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) is prepared and optimized for application in solvent-free solid-state supercapacitors. The synthesized gel polymer electrolyte exhibits a high ionic conductivity over a wide temperature range (from ∼5 × 10-4 S cm-1 at -30 °C up to ∼1.5 × 10-2 S cm-1 at 80 °C) with good electrochemical stability window (-2.9 to 2.5 V). Thermal studies confirm that the SN containing gel polymer electrolyte remains stable in the same gel phase over a wide temperature range from -30 to 90 °C. The electric double layer capacitors (EDLCs) have been fabricated using activated carbon as active materials and new gel polymer electrolytes. Electrochemical performance of the EDLCs is assessed through cyclic voltammetry, galvanostatic charge-discharge cycling and impedance spectroscopy. The EDLC cells with the proper SN-containing gel polymer electrolyte has been found to give high specific capacitance 176 F g-1 at 0.18 A g-1 and 138 F g-1 at 8 A g-1. These solid-state EDLC cells show good cycling stability and the capability to retain ∼80% of the initial capacitance after 10,000 cycles.

  20. Phase Transitions of Triflate-Based Ionic Liquids under High Pressure.

    PubMed

    Faria, Luiz F O; Ribeiro, Mauro C C

    2015-11-01

    Raman spectroscopy has been used to study phase transitions of ionic liquids based on the triflate anion, [TfO](-), as a function of pressure or temperature. Raman spectra of ionic liquids containing the cations 1-butyl-3-methylimidazolium, [C4C1Im](+), 1-octyl-3-methylimidazolium, [C8C1Im](+), 1-butyl-2,3-dimethylimidazolium, [C4C1C1Im](+), and 1-butyl-1-methylpyrrolidinium, [C4C1Pyr](+), were compared. Vibrational frequencies and binding energy of ionic pairs were calculated by quantum chemistry methods. The ionic liquids [C4C1Im][TfO] and [C4C1Pyr][TfO] crystallize at 1.0 GPa when the pressure is increased in steps of ∼ 0.2 GPa from the atmospheric pressure, whereas [C8C1Im][TfO] and [C4C1C1Im][TfO] do not crystallize up to 2.3 GPa of applied pressure. The low-frequency range of the Raman spectrum of [C4C1Im][TfO] indicates that the system undergoes glass transition, rather than crystallization, when the pressure applied on the liquid has been increased above 2.0 GPa in a single step. Strong hysteresis of spectral features (frequency shift and bandwidth) of the high-pressure crystalline phase when the pressure was released stepwise back to the atmospheric pressure has been found .

  1. [Effects of imidazolium chloride ionic liquids on the acute toxicity and weight of earthworm].

    PubMed

    Huang, Ruo-Nan; Fan, Jun-Jie; Tu, Hong-Zhi; Tang, Ling-Yan; Liu, Hui-Jun; Xu, Dong-Mei

    2013-04-01

    Standard contact filter paper test of OECD and artificial soil test were used to study the acute lethal effect of three imidazolium chloride ionic liquids, 1-butyl- 3-methylimidazolium chloride ([Bmim] Cl), 1-hexyl- 3-methylimidazolium chloride ([Hmim] Cl), and 1-octyl- 3-methylimidazolium chloride ([Omim] Cl) on earthworm (Eisenia fetida), and the weight of the earthworms was measured after subtle exposure. The 24 h-LC50 values of [Bmim] Cl, [Hmim] Cl and [Omim] Cl using the contact filter paper method were 109.60, 50.38 and 7.94 microg x cm(-2), respectively. The 48 h-LC50 values were 98.52, 39.14 and 3.61 microg x cm(-2), respectively. Using the artificial soil method, the 7 d-LC50 values of [Bmim] Cl, [Hmim] Cl and [Omim] Cl were 447.78, 245.56 and 180.51 mg x kg(-1), respectively, and the 14 d-LC50 values were 288.42, 179.75, 150.35 mg x kg(-1), respectively. There were differences in poisoning symptoms of the three ionic liquids on earthworms. The growth of Eisenia fetida was inhibited and declined with increasing ionic liquid concentration. The toxicity of ionic liquids on Eisenia fetida increased with the length of carbon chain.

  2. Direct Synthesis of Controlled-Size Nanospheres inside Nanocavities of Self-Organized Photopolymerizing Soft Oxometalates [PW12 O40 ]n (n=1100-7500).

    PubMed

    Das, Kousik; Roy, Soumyajit

    2015-09-01

    The unusual self-assembly of {(BMIm)2 (DMIm)[PW12 O40 ]}n (n=1100-7500) (BMIm=1-butyl-3-methylimidazolium, DMIm=3,3'-dimethyl-1,1'-diimidazolium) soft oxometalates (SOMs) with controlled size and a hollow nanocavity was exploited for the photochemical synthesis of polymeric nanospheres within the nanocavity of the SOM. The SOM vesicle has been characterized by using several techniques, including dynamic light scattering (DLS), static light scattering (SLS), attenuated total reflection (ATR) IR spectroscopy, Raman spectroscopy, microscopy, and zeta-potential analysis. The self-assembly and stabilization of this soft-oxometalate vesicle has been shown by means of counter-ion condensation. The immediate implication of such stabilization-the variation of the dielectric constant with the hydrodynamic radius of the vesicle-has been used to synthesize vesicles of controlled size. Such vesicles of varying size have been used as templates for polymerization reactions that produce polymeric spheres of controlled size. Direct evidence shows that the SOM behaves as a model heterogeneous catalytic system. Such surfactant- and initiator-free photochemical synthetic routes for obtaining uniform latex spheres could be used in the making of optical bandgap materials, inverse opals, and paints. PMID:26185037

  3. Ionic liquid assisted chemical strategy to TiO2 hollow nanocube assemblies with surface-fluorination and nitridation and high energy crystal facet exposure for enhanced photocatalysis.

    PubMed

    Yu, Shengli; Liu, Baocang; Wang, Qin; Gao, Yuxi; Shi, Ying; Feng, Xue; An, Xiaoting; Liu, Lixia; Zhang, Jun

    2014-07-01

    Realization of anionic nonmetal doping and high energy crystal facet exposure in TiO2 photocatalysts has been proven to be an effective approach for significantly improving their photocatalytic performance. A facile strategy of ionic liquid assisted etching chemistry by simply hydrothermally etching hollow TiO2 spheres composed of TiO2 nanoparticles with an ionic liquid of 1-butyl-3-methylimidazolium tetrafluoroborate without any other additives is developed to create highly active anatase TiO2 nanocubes and TiO2 nanocube assemblies. With this one-pot ionic liquid assisted etching process, the surface-fluorination and nitridation and high energy {001} crystal facets exposure can be readily realized simultaneously. Compared with the benchmark materials of P25 and TiO2 nanostructures with other hierarchical architectures of hollow spheres, flaky spheres, and spindles synthesized by hydrothermally etching hollow TiO2 spheres with nonionic liquid of NH4F, the TiO2 nanocubes and TiO2 nanocube assemblies used as efficient photocatalysts show super high photocatalytic activity for degradation of methylene blue, methyl orange, and rhodamine B, due to their surface-fluorination and nitridation and high energy crystal facet exposure. The ionic liquid assisted etching chemistry is facile and robust and may be a general strategy for synthesizing other metal oxides with high energy crystal facets and surface doping for improving photocatalytic activity. PMID:24881462

  4. Electron microscopy of Staphylococcus epidermidis fibril and biofilm formation using image-enhancing ionic liquid.

    PubMed

    Takahashi, Chisato; Kalita, Golap; Ogawa, Noriko; Moriguchi, Keiichi; Tanemura, Masaki; Kawashima, Yoshiaki; Yamamoto, Hiromitsu

    2015-02-01

    We established an optimized biofilm observation method using a hydrophilic ionic liquid (IL), 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF4]). In the present study, a biofilm was formed by Staphylococcus epidermidis. Using field emission (FE) scanning electron microscopy (SEM) and transmission electron microscopy (TEM), the colonization of assemblages formed by microbial cells was observed as a function of the cultivation time. FE-TEM analysis revealed that the fibril comprises three types of protein. In addition, the ultrastructure of each protein monomer was visualized. It was expected that the curly-structured protein plays an important role in extension during fibril formation. Compared to the conventional sample preparation method for electron microscopy, a fine structure was easily obtained by the present method using IL. This observation technique can provide valuable information to characterize the ultrastructure of the fibril and biofilm that has not been revealed till date. Furthermore, these findings of the molecular architecture of the fibril and the colonization behavior of microbial cells during biofilm formation are useful for the development of antibacterial drugs and microbial utilization.

  5. Molecular dynamics studies on the adaptability of an ionic liquid in the extraction of solid nanoparticles.

    PubMed

    Frost, Denzil S; Machas, Michael; Dai, Lenore L

    2012-10-01

    Recently, a number of publications have suggested that ionic liquids (ILs) can absorb solid particles. This development may have implications in fields like oil sand processing, oil spill beach cleanup, and water treatment. In this Article, we provide a computational investigation of this phenomenon via molecular dynamics simulations. Two particle surface chemistries were investigated: (1) hydrocarbon-saturated and (2) silanol-saturated, representing hydrophobic and hydrophilic particles, respectively. Employing 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF(6)]) as a model IL, these nanoparticles were allowed to equilibrate at the IL/water and IL/hexane interfaces to observe the interfacial self-assembled structures. At the IL/water interface, the hydrocarbon-based nanoparticles were nearly completely absorbed by the IL, while the silica nanoparticles maintained equal volume in both phases. At the IL/hexane interface, the hydrocarbon nanoparticles maintained minimal interactions with the IL, whereas the silica nanoparticles were nearly completely absorbed by it. Studies of these two types of nanoparticles immersed in the bulk IL indicate that the surface chemistry has a great effect on the corresponding IL liquid structure. These effects include layering of the ions, hydrogen bonding, and irreversible absorption of some ions to the silica nanoparticle surface. We quantify these effects with respect to each nanoparticle. The results suggest that ILs likely exhibit this absorption capability because they can form solvation layers with reduced dynamics around the nanoparticles. PMID:22950605

  6. Comparing an ionic liquid to a molecular solvent in the cesium cation extraction by a calixarene: a molecular dynamics study of the aqueous interfaces.

    PubMed

    Sieffert, Nicolas; Wipff, Georges

    2006-10-01

    We report a molecular dynamics (MD) study of the interfacial behavior of key partners involved in the Cs(+) cation extraction by a calix[4]arene-crown-6 host (L), comparing an ionic liquid (IL) to a classical molecular solvent (chloroform) as receiving "oil" phase. The IL is composed of hydrophobic 1-butyl-3-methylimidazolium cations (BMI(+)) and bis(trifluoromethylsulfonyl)imide anions (Tf(2)N(-)) and forms a biphasic system with water. The simulations reveal similarities but also interesting differences between the two types of interfaces. Much longer times are needed to "equilibrate" IL systems, compared to classical liquid mixtures, and there is more intersolvent mixing with the IL than with chloroform, especially concerning the water-in-oil content. There is also some excess of the BMI(+) cations over the Tf(2)N(-) anions in the aqueous phase. Simulations on the Na(+)NO(3)(-) and Cs(+)NO(3)(-) ions show that they sometimes interact at the interface with the IL ions, forming hydrated intimate ion pairs, whereas they are "repelled" by the classical interface. The LCs(+) complex and L ligand also behave differently, depending on the "oil phase". They are better solvated by the IL than by chloroform and thus poorly attracted at the IL interface, whereas they adsorb at the chloroform interface, adopting well-defined amphiphilic orientations. The results are discussed in the context of assisted ion transfer and provide a number of arguments explaining the specificity and efficiency of IL based, compared to classical extraction systems. PMID:17004811

  7. Ionic liquid-based aqueous two-phase system extraction of sulfonamides in milk.

    PubMed

    Shao, Mingyuan; Zhang, Xuli; Li, Na; Shi, Jiayuan; Zhang, Huijie; Wang, Zhibing; Zhang, Hanqi; Yu, Aimin; Yu, Yong

    2014-06-15

    A simple method for the determination of six sulfonamides (SAs) in milk samples was developed. 1-Butyl-3-methylimidazolium tetrafluoroborate and trisodium citrate dihydrate were used to form aqueous two-phase system. The aqueous two phase system was applied to the extraction of the SAs and the determination of the analytes was performed by high-performance liquid chromatography. To achieve optimum extraction performance, several experimental parameters, including the type and the amount of salt, the type and amount of ionic liquid, ultrasonic time and pH of sample solution, were investigated and optimized. Under the optimal experimental conditions, good linearity was observed in the range of 8.55-1036.36ngmL(-1). The limits of detection and quantification were in the range of 2.04-2.84 and 6.73-9.37ngmL(-1), respectively. The present method was successfully applied to the determination of SAs in milk samples, and the recoveries of analytes were in the range of 72.32-108.96% with relative standard deviations ranging from 0.56 to 12.20%. The results showed that the present method was rapid, feasible and environmentally friendly. PMID:24854709

  8. Role of the Hofmeister series in the formation of ionic-liquid-based aqueous biphasic systems.

    PubMed

    Shahriari, Shahla; Neves, Catarina M S S; Freire, Mara G; Coutinho, João A P

    2012-06-21

    Among the numerous and interesting features of ionic liquids is their ability to form aqueous biphasic systems (ABSs) when combined with inorganic or organic salts in aqueous media. In this work, a wide range of salts was studied, aiming at gathering a detailed picture on the molecular mechanisms that govern the ability of the salt ions to induce the formation of ionic-liquid-based ABSs. For that purpose, 1-butyl-3-methylimidazolium trifluoromethanesulfonate was chosen due to its facility to undergo liquid-liquid demixing in aqueous media containing conventional salts. The corresponding ternary phase diagrams, tie-lines, and tie-line lengths were determined at 298 K and atmospheric pressure. With the large body of data measured in this work, it was possible to establish a scale on the salt cation and anion abilities to induce the formation of ionic-liquid-based ABSs, which follows the Hofmeister series, and to show that the molar entropy of hydration of the salt ions is the driving force for aqueous two-phase system formation. PMID:22594382

  9. ILs-based microwave-assisted extraction coupled with aqueous two-phase for the extraction of useful compounds from Chinese medicine.

    PubMed

    Lin, Xiao; Wang, Yuzhi; Liu, Xiaojie; Huang, Songyun; Zeng, Qun

    2012-09-01

    Ionic liquids-based microwave-assisted extraction (ILs-MAE) of medicinal or useful compounds from plants was investigated as an alternative to conventional organic solvent extractions. The extraction and the preconcentration of aqueous two-phase (ATP) systems have been integrated. Various operating parameters were systematically considered by single-factor and L(9) (3(4)) orthogonal array experiments. 1-Butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF(4)]) has been selected to extract Apocynum venetum. The extract was then converted to the top phase by [bmim][BF(4)]/NaH(2)PO(4) system which was suitable for the preconcentration. Reversed phase high performance liquid chromatography (RP-HPLC) with ultraviolet detection was employed for the analysis of hyperin and isoquercitrin in Apocynum venetum. The optimal experiment approach could provide higher detection limit of hyperin and isoquercitrin which were 3.82 μg L(-1) and 3.00 μg L(-1) in Apocynum venetum. The recoveries of hyperin and isoquercitrin were 97.29% (RSD = 1.02%) and 99.40% (RSD = 1.13%), respectively, from aqueous samples of Apocynum venetum by the proposed method. Moreover, the extraction mechanism of ILs-MAE and the microstructures and chemical structures of the herb before and after extraction were also investigated. The method exhibited potential applicability with other complicated samples. PMID:22785248

  10. Extraction of proteins from biological fluids by use of an ionic liquid/aqueous two-phase system.

    PubMed

    Du, Zhuo; Yu, Yong-Liang; Wang, Jian-Hua

    2007-01-01

    An ionic liquid/aqueous two-phase system based on the hydrophilic ionic liquid 1-butyl-3-methylimidazolium chloride (BmimCl) and K(2)HPO(4) has been employed for direct extraction of proteins from human body fluids for the first time. Proteins present at low levels were quantitatively extracted into the BmimCl-rich upper phase with a distribution ratio of about 10 between the upper and lower phase and an enrichment factor of 5. Addition of an appropriate amount of K(2)HPO(4) to the separated upper phase results in a further phase separation, giving rise to an improved enrichment factor of 20. FTIR and UV spectroscopy demonstrated that no chemical (bonding) interactions between the ionic liquid and the protein functional groups were identifiable, while no alterations of the natural properties of the proteins were observed. The partitioning of proteins in the two-phase system was assumed to have been facilitated by the electrostatic potential difference between the coexisting phases, as well as by salting out effects. The system could be applied successfully for the quantification of proteins in human urine after on-line phase separation in a flow system. The use of an ionic liquid, as a green solvent, offers clear advantages over traditional liquid-liquid extractions, in which the use of toxic organic solvents is unavoidable. PMID:17136782

  11. Extraction of testosterone and epitestosterone in human urine using aqueous two-phase systems of ionic liquid and salt.

    PubMed

    He, Chiyang; Li, Shehong; Liu, Huwei; Li, Kean; Liu, Feng

    2005-08-01

    Based on aqueous two-phase systems (ATPS) consisting of 1-butyl-3-methylimidazolium chloride, a hydrophilic ionic liquid (IL), and K2HPO4, a new and simple extraction technique, coupled with a reversed-phase high performance liquid chromatography (RP-HPLC), was developed for the simultaneous concentration and analysis of testosterone (T) and epitestosterone (ET) in human urine. Under the optimal conditions, the extraction efficiencies for both analytes were 80-90% in a one-step extraction. The method required only 3.0 mL of urine and a single hydrolysis/deproteinization/extraction step followed by direct injection of the IL-rich upper phase into HPLC system for analysis. The method has been satisfactorily applied to the analysis of T and ET in human urine with detection limits of 1 ng/mL and linear ranges of 10-500 ng/mL for both compounds. Compared with conventional liquid-liquid extraction or solid phase extraction, this new method is much "greener" due to no use of volatile organic solvent and low consumption of IL. The proposed extraction technique opens up new possibilities in the separation of other drugs. PMID:16035355

  12. Synthesis of Mesoporous Carbons from Rice Husk for Supercapacitors with High Energy Density in Ionic Liquid Electrolytes.

    PubMed

    He, Xiaojun; Zhang, Hebao; Xie, Kang; Xia, Youyi; Zhao, Zhigang; Wang, Xiaoting

    2016-03-01

    High-performance mesoporous carbons (MCs) for supercapacitors were made from rice husk by one-step microwave-assisted ZnCl2 activation. The microstructures of MCs as-made were characterized by field emission scanning electron microscopy and transmission electron microscopy. The pore structure parameters of MCs were obtained by N2 adsorption technique. The electrochemical properties of MC electrodes were studied by constant current charge-discharge, cyclic voltammetry and electrochemical impedance spectroscopy in different electrolytes. The results showed that the specific surface area of MC4 made at the ZnCl2/rice husk mass of 4:1 reached 1737 m2 g(-1). The specific capacitance and energy density of the electrodes fabricated from the mixture of MC4 and microporous carbon increased with the mass percentage of MC4, reaching 157 F g(-1) and 84 Wh kg(-1) at 0.05 A g(-1), and showed good cycle stability in 1-butyl-3-methylimidazolium hexafluorophosphate electrolyte. Compared to the often-used aqueous and organic electrolytes, MC4 capacitor exhibited extremely high energy density in ionic liquid electrolyte, remaining at 28 Wh kg(-1) at 1684 W kg(-1). This work paves a new way to produce cost-effective MCs from biomass for supercapacitors with extremely high energy density in ionic liquid electrolytes.

  13. Influence of PVP template on the formation of porous TiO2 nanofibers by electrospinning technique for dye-sensitized solar cell

    NASA Astrophysics Data System (ADS)

    Elayappan, Vijayakumar; Panneerselvam, Pratheep; Nemala, Sivasankar; Nallathambi, Karthick S.; Angaiah, Subramania

    2015-09-01

    The porous TiO2 nanofibers were prepared by electrospinning technique using polyvinylpyrrolidone (PVP) as template as well as pore-forming agent at the calcination temperature of 475 °C for 5 h. The influence of various concentrations of PVP (5, 8 and 10 wt%) on the surface area and porosity of the prepared TiO2 nanofibers (NFs) were studied by using BET-specific surface area analyzer. The TiO2 NFs obtained by using 5 wt% of PVP had higher surface area and porosity than those obtained by using 8 and 10 wt% of PVP. The prepared electrospun TiO2 NFs were characterized by using TG analysis, X-ray diffraction, FTIR, FE-SEM and TEM studies. Finally, dye-sensitized solar cells were assembled using the prepared TiO2 NFs as the photoanode, Pt as the cathode and 0.5 M 1-butyl-3-methylimidazolium iodide, 0.5 M LiI, 0.05 M I2, 0.5 M 4-tertbutylpyridine in acetonitrile as an electrolyte. Among the three photoanodes, the cell assembled using porous TiO2 NFs obtained by using 5 wt% of PVP showed higher power conversion efficiency (PCE) of 4.81 % than those obtained by using 8 and 10 wt% of PVP, which showed the lower PCE of 4.13 and 3.42 %, respectively.

  14. Influence of ionic liquid film thickness on ion pair distributions and orientations at graphene and vacuum interfaces.

    PubMed

    Wang, Yong-Lei; Laaksonen, Aatto; Lu, Zhong-Yuan

    2013-08-28

    Microscopic structures, orientational preferences together with mass, number and electron density distributions of 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]) ionic liquid (IL) have been studied on a neutral hydrophobic graphene surface, and at the IL-vacuum interface using atomistic Molecular Dynamics simulations. At the IL-graphene interface, distinct mass, number and electron density distributions are observed oscillating into the bulk region with several compact structural layers. The imidazolium ring of [BMIM] cations lies preferentially flat on the graphene surface, with its methyl and butyl side chains elongated along the graphene surface. At the IL-vacuum interface, however, the distributions of [BMIM][PF6] ion pairs are strongly influenced by the thickness of IL film. With the increase of IL film thickness, the orientations of [BMIM] cations at the IL-vacuum interface change gradually from dominant flat distributions along the graphene surface to orientations where the imidazolium rings are either parallel or perpendicular to the IL-vacuum interface with tilted angles. The outmost layers are populated with alkyl groups and imparted with distinct hydrophobic character. The calculated radial distribution functions suggest that ionic structures of [BMIM][PF6] ion pairs in IL-graphene and IL-vacuum interfacial regions are significantly different from each other and also from that in bulk regions.

  15. Charge engineering of cellulases improves ionic liquid tolerance and reduces lignin inhibition.

    PubMed

    Nordwald, Erik M; Brunecky, Roman; Himmel, Michael E; Beckham, Gregg T; Kaar, Joel L

    2014-08-01

    We report a novel approach to concurrently improve the tolerance to ionic liquids (ILs) as well as reduce lignin inhibition of Trichoderma reesei cellulase via engineering enzyme charge. Succinylation of the cellulase enzymes led to a nearly twofold enhancement in cellulose conversion in 15% (v/v) 1-butyl-3-methylimidazolium chloride ([BMIM][Cl]). The improvement in activity upon succinylation correlated with the apparent preferential exclusion of the [Cl] anion in fluorescence quenching assays. Additionally, modeling analysis of progress curves of Avicel hydrolysis in buffer indicated that succinylation had a negligible impact on the apparent KM of cellulase. As evidence of reducing lignin inhibition of T. reesei cellulase, succinylation resulted in a greater than twofold increase in Avicel conversion after 170 h in buffer with 1 wt% lignin. The impact of succinylation on lignin inhibition of cellulase further led to the reduction in apparent KM of the enzyme cocktail for Avicel by 2.7-fold. These results provide evidence that naturally evolved cellulases with highly negative surface charge densities may similarly repel lignin, resulting in improved cellulase activity. Ultimately, these results underscore the potential of rational charge engineering as a means of enhancing cellulase function and thus conversion of whole biomass in ILs. PMID:24522957

  16. Hydrothermal microwave valorization of eucalyptus using acidic ionic liquid as catalyst toward a green biorefinery scenario.

    PubMed

    Xu, Ji-Kun; Chen, Jing-Huan; Sun, Run-Cang

    2015-10-01

    The application of the acidic ionic liquid (IL), 1-butyl-3-methylimidazolium hydrogensulfate ([bmim]HSO4), as a catalyst in the hydrothermal microwave treatment (HMT) and green upgradation of eucalyptus biomass has been investigated. The process was carried out in a microwave reactor system at different temperatures (140-200°C) and evaluated for severities. The xylooligosaccharides (XOS, refers to a DP of 2-6) yield up to 5.04% (w/w) of the initial biomass and 26.72% (w/w) of xylan were achieved. Higher temperature resulted in lower molecular weight product, and enhanced the concentration of monosaccharides and byproducts. The morphology and structure of the solid residues were performed using an array of techniques, such as SEM, XRD, FTIR, BET surface area, and CP/MAS (13)C NMR, by which the increase of crystallinity, the destruction of surface structure, and the changes in functional groups and compositions were studied after the pretreatment, thus significantly enhancing the enzymatic hydrolysis.

  17. Ionic liquid and aqueous two-phase extraction based on salting-out coupled with high-performance liquid chromatography for the determination of seven rare ginsenosides in Xue-Sai-Tong injection.

    PubMed

    Li, Lan-Jie; Jin, Yong-Ri; Wang, Xiao-Zhong; Liu, Ying; Wu, Qian; Shi, Xiao-Lei; Li, Xu-Wen

    2015-09-01

    A method of ionic liquid salt aqueous two-phase extraction coupled with high-performance liquid chromatography has been developed for the analysis of seven rare ginsenosides including Rg6 , F4 , 20(S)-Rg3 , 20(R)-Rg3 , Rk3 , Rk1 , and Rg5 in Xue-Sai-Tong injection. The injection was mixed with ionic liquid 1-butyl-3-methylimidazolium bromide aqueous solution, and a mixture was obtained. With the addition of sodium dodecyl sulfate and dipotassium phosphate into the mixture, the aqueous two-phase mixture was formed after ultrasonic treatment and centrifuged. Rare ginsenosides were extracted into the upper phase. To obtain a high extraction factors, various influences were considered systematically, such as the volume of ionic liquid, the category and amount of salts, the amount of sodium dodecyl sulfate, the pH value of system, and the time of ultrasonic treatment. Under the optimal condition, rare ginsenosides in Xue-Sai-Tong injection were enriched and detected, the recoveries of seven rare ginsenosides ranged from 90.05 to 112.55%, while relative standard deviations were lower than 2.50%. The developed method was reliable, rapid and sensitive for the determination of seven rare ginsenosides in the injections. PMID:26081987

  18. Matrix solid-phase dispersion coupled with magnetic ionic liquid dispersive liquid-liquid microextraction for the determination of triazine herbicides in oilseeds.

    PubMed

    Wang, Yuanpeng; Sun, Ying; Xu, Bo; Li, Xinpei; Wang, Xinghua; Zhang, Hanqi; Song, Daqian

    2015-08-12

    A novel method was developed for the determination of six triazine herbicides from oilseeds by matrix solid-phase dispersion combined with magnetic ionic liquid dispersive liquid-liquid microextraction (MSPD-MIL-DLLME), followed by ultrafast liquid chromatography with ultraviolet detection (UFLC-UV). The MIL, 1-butyl-3-methylimidazolium tetrachloroferrate ([C4mim][FeCl4]), was used as the microextraction solvent to simplify the extraction procedure by magnetic separation. The effects of several important experimental parameters, including type of dispersant, ratio of sample to dispersant, type and volume of collected elution solvent, type and volume of MIL, were investigated. Using the present method, UFLC-UV gave the limits of detection (LODs) of 1.20-2.72 ng g(-1) and the limits of quantification (LOQs) of 3.99-9.06 ng g(-1) for triazine herbicides. The recoveries were ranged from 82.9 to 113.7% and the relative standard deviations (RSDs) were equal or lower than 7.7%. The present method is easy-to-use and effective for extraction of triazine herbicides from oilseeds and shows the potentials of practical applications in the treatment of the fatty solid samples. PMID:26320960

  19. Catalysis of rice straw hydrolysis by the combination of immobilized cellulase from Aspergillus niger on β-cyclodextrin-Fe3O4 nanoparticles and ionic liquid.

    PubMed

    Huang, Po-Jung; Chang, Ken-Lin; Hsieh, Jung-Feng; Chen, Shui-Tein

    2015-01-01

    Cellulase from Aspergillus niger was immobilized onto β-cyclodextrin-conjugated magnetic particles by silanization and reductive amidation. The immobilized cellulase gained supermagnetism due to the magnetic nanoparticles. Ninety percent of cellulase was immobilized, but the activity of immobilized cellulase decreased by 10%. In this study, ionic liquid (1-butyl-3-methylimidazolium chloride) was introduced into the hydrolytic process because the original reaction was a solid-solid reaction. The activity of immobilized cellulase was improved from 54.87 to 59.11 U g immobilized cellulase(-1) at an ionic liquid concentration of 200 mM. Using immobilized cellulase and ionic liquid in the hydrolysis of rice straw, the initial reaction rate was increased from 1.629 to 2.739 g h(-1) L(-1). One of the advantages of immobilized cellulase is high reusability--it was usable for a total of 16 times in this study. Compared with free cellulase, magnetized cellulase can be recycled by magnetic field and the activity of immobilized cellulase was shown to remain at 85% of free cellulase without denaturation under a high concentration of glucose (15 g L(-1)). Therefore, immobilized cellulase can hydrolyze rice straw continuously compared with free cellulase. The amount of harvested glucose can be up to twentyfold higher than that from the hydrolysis by free cellulase. PMID:25874210

  20. Two solid-phase recycling method for basic ionic liquid [C4mim]Ac by macroporous resin and ion exchange resin from Schisandra chinensis fruits extract.

    PubMed

    Ma, Chun-hui; Zu, Yuan-gang; Yang, Lei; Li, Jian

    2015-01-22

    In this study, two solid-phase recycling method for basic ionic liquid (IL) 1-butyl-3-methylimidazolium acetate ([C4mim]Ac) were studied through a digestion extraction system of extracting biphenyl cyclooctene lignans from Schisandra chinensis. The RP-HPLC detection method for [C4mim]Ac was established in order to investigate the recovery efficiency of IL. The recycling method of [C4mim]Ac is divided into two steps, the first step was the separation of lignans from the IL solution containing HPD 5000 macroporous resin, the recovery efficiency and purity of [C4mim]Ac achieved were 97.8% and 67.7%, respectively. This method cannot only separate the lignans from [C4mim]Ac solution, also improve the purity of lignans, the absorption rate of lignans in [C4mim]Ac solution was found to be higher (69.2%) than that in ethanol solution (57.7%). The second step was the purification of [C4mim]Ac by the SK1B strong acid ion exchange resin, an [C4mim]Ac recovery efficiency of 55.9% and the purity higher than 90% were achieved. Additionally, [C4mim]Ac as solvent extraction of lignans from S. chinensis was optimized, the hydrolysis temperature was 90°C and the hydrolysis time was 2h. PMID:25463641

  1. Hydrothermal microwave valorization of eucalyptus using acidic ionic liquid as catalyst toward a green biorefinery scenario.

    PubMed

    Xu, Ji-Kun; Chen, Jing-Huan; Sun, Run-Cang

    2015-10-01

    The application of the acidic ionic liquid (IL), 1-butyl-3-methylimidazolium hydrogensulfate ([bmim]HSO4), as a catalyst in the hydrothermal microwave treatment (HMT) and green upgradation of eucalyptus biomass has been investigated. The process was carried out in a microwave reactor system at different temperatures (140-200°C) and evaluated for severities. The xylooligosaccharides (XOS, refers to a DP of 2-6) yield up to 5.04% (w/w) of the initial biomass and 26.72% (w/w) of xylan were achieved. Higher temperature resulted in lower molecular weight product, and enhanced the concentration of monosaccharides and byproducts. The morphology and structure of the solid residues were performed using an array of techniques, such as SEM, XRD, FTIR, BET surface area, and CP/MAS (13)C NMR, by which the increase of crystallinity, the destruction of surface structure, and the changes in functional groups and compositions were studied after the pretreatment, thus significantly enhancing the enzymatic hydrolysis. PMID:26119053

  2. Toxicity of two imidazolium ionic liquids, [bmim][BF4] and [omim][BF4], to standard aquatic test organisms: Role of acetone in the induced toxicity.

    PubMed

    Tsarpali, Vasiliki; Dailianis, Stefanos

    2015-07-01

    The main goal of this study was to investigate the toxicity of the imidazolium-based ionic liquids (ILs), [bmim][BF4] (1-butyl-3-methylimidazolium tetrafluoroborate) and [omim][BF4] (1-octyl-3-methylimidazolium tetrafluoroborate), in battery of standard aquatic toxicity test organisms. Specifically, exposure of the algae Scenedesmus rubescens, crustaceans Thamnocephalus platyurus and Artemia franciscana, rotifers Brachionus calyciflorus and Brachionus plicatilis and bivalve Mytilus galloprovincialis to different concentrations of [bmim][BF4], [omim][BF4] and/or a binary mixture of [bmim][BF4]-[omim][BF4] (1:1) with or without acetone (carrier solvent), revealed that solvent can differentially mediate ILs' toxic profile. Acetone's ability to differentially affect ILs' cation's alkyl chain length, as well as the hydrolysis of [BF4(-)] anions was evident. Given that the toxic potency of the tested ILs seemed to be equal or even higher (in some cases) than those of conventional organic solvents, the present study revealed that the characterization of imidazolium-based ILs as "green solvents" should not be generalized, at least in case of their natural occurrence in mixtures with organic solvents, such as acetone. PMID:25839183

  3. Ionic Liquid-Assisted Hydrothermal Method Synthesis of Flower-Like MoS2 and Their Electrochemical Performances.

    PubMed

    Li, Maohua; Yang, Bo; Hao, Junying; Lu, Yi; Long, Zerong; Liu, Yumei

    2016-06-01

    Molybdenum disulfide (MoS2) was prepared successfully via hydrothermal reaction at 200 degrees C in water/ethanol (1:1) solvent system using the ammonium molybdate and sodium thiosulfate as the molybdenum sources and sulfur sources, 1-butyl-3-methylimidazolium chloride salt [BMIM][Cl] as the additive agent. The scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to examine the morphology and structure of flower-like products. X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy spectrum analysis results show that the as-prepared product is a pure phase of MoS2. The prepared products are used as electrode materials for Li-ion batteries and showed excellent cycle stability and high Coulombic efficiency at a current density of 200 mA x g(-1) in the voltage range of 0.01 - 3.00 V (vs. Li/Li+). In addition, this paper also examined the influence of the reaction time and the amount of template agent on morphology, and discussed the reaction mechanism of the formation of flower-like morphology. PMID:27427696

  4. Dissociation of equimolar mixtures of aqueous carboxylic acids in ionic liquids: role of specific interactions.

    PubMed

    Shukla, Shashi Kant; Kumar, Anil

    2015-04-30

    Hammett acidity function observes the effect of protonation/deprotonation on the optical density/absorbance of spectrophotometric indicator. In this work, the Hammett acidity, H0, of equimolar mixtures of aqueous HCOOH, CH3COOH, and CH3CH2COOH was measured in 1-methylimidazolium-, 1-methylpyrrolidinium-, and 1-methylpiperidinium-based protic ionic liquids (PILs) and 1-butyl-3-methylimidazolium-based aprotic ionic liquid (AIL) with formate (HCOO(-)) anion. Higher H0 values were observed for the equimolar mixtures of aqueous carboxylic acids in protic ionic liquids compared with those of the aprotic ionic liquid because of the involvement of the stronger specific interactions between the conjugate acid of ionic liquid and conjugate base of carboxylic acids as suggested by the hard-soft acid base (HSAB) theory. The different H0 values for the equimolar mixtures of aqueous carboxylic acids in protic and aprotic ionic liquids were noted to depend on the activation energy of proton transfer (Ea,H(+)). The higher activation energy of proton transfer was obtained in AIL, indicating lower ability to form specific interactions with solute than that of PILs. Thermodynamic parameters determined by the "indicator overlapping method" further confirmed the involvement of the secondary interactions in the dissociation of carboxylic acids. On the basis of the thermodynamic parameter values, the potential of different ionic liquids in the dissociation of carboxylic acids was observed to depend on the hydrogen bond donor acidity (α) and hydrogen bond acceptor basicity (β), characteristics of specific interactions.

  5. Development of an ionic liquid-based microwave-assisted method for the extraction and determination of taxifolin in different parts of Larix gmelinii.

    PubMed

    Liu, Zaizhi; Jia, Jia; Chen, Fengli; Yang, Fengjian; Zu, Yuangang; Yang, Lei

    2014-01-01

    An ionic liquid-based microwave-assisted extraction method (ILMAE) was successfully applied for the extraction of taxifolin from Larix gmelinii. Different kinds of 1-alkyl-3-methylimidazolium ionic liquids with different kinds of cations and anions were studied and 1-butyl-3-methylimidazolium bromide was chosen as the optimal solvent for taxifolin extraction. The optimal conditions of ILMAE were determined by single factor experiments and Box-Behnken design as follows: [C4mim]Br concentration of 1.00 M, soaking time of 2 h, liquid-solid ratio of 15:1 mL/g, microwave irradiation power of 406 W, microwave irradiation time of 14 min. No degradation of taxifolin had been observed under the optimum conditions as evidenced from the stability studies performed with standard taxifolin. Compared with traditional solvent and methods, ILMAE provided higher extraction yield, lower energy and time consumption. The distribution of taxifolin in different parts of larch and the influences of age, orientation, and season on the accumulation of taxifolin were analyzed for the sufficient utilization of L. gmelinii.

  6. Direct UV-spectroscopic measurement of selected ionic-liquid vapors

    SciTech Connect

    Dai, Sheng; Luo, Huimin; Wang, Congmin; Li, Haoran

    2010-01-01

    The hallmark of ionic liquids lies in their negligible vapor pressure. This ultralow vapor pressure makes it difficult to conduct the direct spectroscopic measurement of ionic-liquid vapors. In fact, there have been no electronic spectroscopic data currently available for ionic-liquid vapors. This deficiency significantly hampers the fundamental understanding of the unique molecular structures of ionic liquids. Herein, the UV absorption spectra of eight ionic liquids, such as 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([Bmim{sup +}] [Tf{sub 2}N{sup -}]) and 1-ethyl-3-methylimidazolium bis(perfluoroethylsulfonyl)imide ([Emim{sup +}][beti{sup -}]) in the vapor phase in a distillation-like environment, were measured through a high-temperature spectroscopic technique to fill this knowledge gap. Two strong absorption peaks of the [Bmim{sup +}][Tf{sub 2}N{sup -}] vapor lie at 202 and 211 nm, slightly different from those of the neat [Bmim{sup +}][Tf{sub 2}N{sup -}] thin film and its solution in water. Based on the quantitative determination of the vapor absorption spectra as a function of temperature, the vaporization enthalpies of these ionic liquids vapors were measured and found to be in good agreement with the corresponding literature values. This in situ method opens up a new avenue to study the nature of ionic-liquid vapors and to determine the vaporization enthalpies of ionic liquids.

  7. New Alkylether-Thiazolium Room-Temperature Ionic Liquid Lubricants: Surface Interactions and Tribological Performance.

    PubMed

    Espinosa, Tulia; Sanes, José; Bermúdez, María-Dolores

    2016-07-20

    The use of newly synthesized alkylether-thiazolium ionic liquids as lubricants is described for the first time. Two ionic liquids composed of a thiazolium cation and a bis(trifluoromethanesulfonyl)amide ([Th][Tf2N]) or dicyanamide ([Th][(NC)2N]) anion have been studied, and their tribological behavior has been compared with that of 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide ([Im][Tf2N]) in pin-on-disk tests using sapphire balls against AISI 52100 or AISI 316L steels. All ionic liquids show higher contact angles on AISI 316L steel than on AISI 52100, the lowest values found for ([Im][Tf2N]) on both steel surfaces. AISI 52100 shows similar friction coefficients for all lubricants, and negligible wear rates for the ionic liquids containing the bis(trifluoromethanesulfonyl)amide anion. Immersion tests show no corrosion of AISI 52100 in imidazolium or thiazolium bis(trifluoromethanesulfonyl)amide ionic liquids. AISI 316L shows similar friction coefficients for both bis(trifluoromethanesulfonyl)amide ionic liquids, but the lowest wear rate is obtained for [Th][Tf2N]. An increase in friction coefficient and wear rate is observed for thiazolium dicyanamide. This increase is related to a tribocorrosion process due to decomposition of the thiazolium cation. XPS shows the formation of iron sulfide on the wear track on AISI 316L after lubrication with thiazolium dicyanamide. No tribocorrosion processes take place for the [Tf2N] ionic liquids.

  8. A roadmap to uranium ionic liquids: anti-crystal engineering.

    PubMed

    Yaprak, Damla; Spielberg, Eike T; Bäcker, Tobias; Richter, Mark; Mallick, Bert; Klein, Axel; Mudring, Anja-Verena

    2014-05-19

    In the search for uranium-based ionic liquids, tris(N,N-dialkyldithiocarbamato)uranylates have been synthesized as salts of the 1-butyl-3-methylimidazolium (C4mim) cation. As dithiocarbamate ligands binding to the UO2(2+) unit, tetra-, penta-, hexa-, and heptamethylenedithiocarbamates, N,N-diethyldithiocarbamate, N-methyl-N-propyldithiocarbamate, N-ethyl-N-propyldithiocarbamate, and N-methyl-N-butyldithiocarbamate have been explored. X-ray single-crystal diffraction allowed unambiguous structural characterization of all compounds except N-methyl-N-butyldithiocarbamate, which is obtained as a glassy material only. In addition, powder X-ray diffraction as well as vibrational and UV/Vis spectroscopy, supported by computational methods, were used to characterize the products. Differential scanning calorimetry was employed to investigate the phase-transition behavior depending on the N,N-dialkyldithiocarbamato ligand with the aim to establish structure-property relationships regarding the ionic liquid formation capability. Compounds with the least symmetric N,N-dialkyldithiocarbamato ligand and hence the least symmetric anions, tris(N-methyl-N-propyldithiocarbamato)uranylate, tris(N-ethyl-N-propyldithiocarbamato)uranylate, and tris(N-methyl-N-butyldithiocarbamato)uranylate, lead to the formation of (room-temperature) ionic liquids, which confirms that low-symmetry ions are indeed suitable to suppress crystallization. These materials combine low melting points, stable complex formation, and hydrophobicity and are therefore excellent candidates for nuclear fuel purification and recovery.

  9. Sulfonic Acid- and Lithium Sulfonate-Grafted Poly(Vinylidene Fluoride) Electrospun Mats As Ionic Liquid Host for Electrochromic Device and Lithium-Ion Battery.

    PubMed

    Zhou, Rui; Liu, Wanshuang; Leong, Yew Wei; Xu, Jianwei; Lu, Xuehong

    2015-08-01

    Electrospun polymer nanofibrous mats loaded with ionic liquids (ILs) are promising nonvolatile electrolytes with high ionic conductivity. The large cations of ILs are, however, difficult to diffuse into solid electrodes, making them unappealing for application in some electrochemical devices. To address this issue, a new strategy is used to introduce proton conduction into an IL-based electrolyte. Poly(vinylidene fluoride-co-hexafluoropropylene) (P(VDF-HFP)) copolymer is functionalized with sulfonic acid through covalent attachment of taurine. The sulfonic acid-grafted P(VDF-HFP) electrospun mats consist of interconnected nanofibers, leading to remarkable improvement in dimensional stability of the mats. IL-based polymer electrolytes are prepared by immersing the modified mats in 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM(+)BF4(-)). It is found that the SO3(-) groups can have Lewis acid-base interactions with the cations (BMIM(+)) of IL to promote the dissociation of ILs, and provide additional proton conduction, resulting in significantly improved ionic conductivity. Using this novel electrolyte, polyaniline-based electrochromic devices show higher transmittance contrast and faster switching behavior. Furthermore, the sulfonic acid-grafted P(VDF-HFP) electrospun mats can also be lithiated, giving additional lithium ion conduction for the IL-based electrolyte, with which Li/LiCoO2 batteries display enhanced C-rate performance.

  10. Green synthesis of polymer monoliths incorporated with carbon nanotubes in room temperature ionic liquid and deep eutectic solvents.

    PubMed

    Zhang, Li-Shun; Gao, Shu-Ping; Huang, Yan-Ping; Liu, Zhao-Sheng

    2016-07-01

    In this work, an efficient method to prepare polymer monoliths with incorporated carbon nanotubes in a mixture of room temperature ionic liquid and deep eutectic solvents was developed. With assistance of the binary green solvent, 1-butyl-3-methylimidazolium tetrafluoroborate and choline chloride/ethylene glycol, single-walled carbon nanotubes were dispersed successfully in pre-polymerization mixture without need of oxidative cutting of carbon nanotubes, which may allow depletion of the emission of volatile organic compounds into environment. The novel single-walled carbon nanotubes monolith was evaluated by capillary electrochromatography. Compared with the monolith made without single-walled carbon nanotubes, the monolith with the incorporation of single-walled carbon nanotubes exhibited high column efficiency (251,000plates/m) in the chromatographic separation. The morphology of the monolith can be tuned by the composition of mixture of ionic liquids and deep eutectic solvents to afford good column permeability and excellent separation ability for small molecules of alkyl phenones and alkyl benzenes. The results demonstrated that the method is a green strategy for the fabrication of multifunctional polymer monoliths.

  11. Efficient adsorption of 1-alkyl-3-methylimidazolium chloride ionic liquids onto modified cellulose microspheres.

    PubMed

    Xu, Min; Ao, Yinyong; Wang, Shuojue; Peng, Jing; Li, Jiuqiang; Zhai, Maolin

    2015-09-01

    A novel sulfonated cellulose microsphere adsorbent (CGS) was prepared by pre-irradiation induced emulsion grafting of glycidyl methacrylate (GMA) onto the cellulose microsphere, followed by sulfonation. The resulting CGS exhibited superior adsorption ability toward 1-alkyl-3-methylimidazolium chloride ([CnMIM]Cl) ionic liquids (ILs). The adsorption equilibrium could be attained rapidly within 40 min for representative 1-butyl-3-methylimidazolium chloride ([C4MIM]Cl) using CGS with different amounts of SO3H group. The adsorption behavior of CGS toward [C4MIM]Cl was well described by the pseudo-second-order model and the Langmuir model. The maximum adsorption capacity toward [C4MIM]Cl was 1.08 mmol/g in the wide range of pH (4.8-10.1). In addition, the adsorption capacity of CGS toward [CnMIM]Cl increased with the alkyl length of cations of [CnMIM]Cl due to the hydrophobic interaction and cation exchange adsorption. Spent CGS could be easily regenerated by 0.1 mol/L HCl or NaCl. The results indicated that this new adsorbent is useful in removing ILs from wastewater.

  12. Two solid-phase recycling method for basic ionic liquid [C4mim]Ac by macroporous resin and ion exchange resin from Schisandra chinensis fruits extract.

    PubMed

    Ma, Chun-hui; Zu, Yuan-gang; Yang, Lei; Li, Jian

    2015-01-22

    In this study, two solid-phase recycling method for basic ionic liquid (IL) 1-butyl-3-methylimidazolium acetate ([C4mim]Ac) were studied through a digestion extraction system of extracting biphenyl cyclooctene lignans from Schisandra chinensis. The RP-HPLC detection method for [C4mim]Ac was established in order to investigate the recovery efficiency of IL. The recycling method of [C4mim]Ac is divided into two steps, the first step was the separation of lignans from the IL solution containing HPD 5000 macroporous resin, the recovery efficiency and purity of [C4mim]Ac achieved were 97.8% and 67.7%, respectively. This method cannot only separate the lignans from [C4mim]Ac solution, also improve the purity of lignans, the absorption rate of lignans in [C4mim]Ac solution was found to be higher (69.2%) than that in ethanol solution (57.7%). The second step was the purification of [C4mim]Ac by the SK1B strong acid ion exchange resin, an [C4mim]Ac recovery efficiency of 55.9% and the purity higher than 90% were achieved. Additionally, [C4mim]Ac as solvent extraction of lignans from S. chinensis was optimized, the hydrolysis temperature was 90°C and the hydrolysis time was 2h.

  13. A novel impedimetric nanobiosensor for low level determination of hydrogen peroxide based on biocatalysis of catalase.

    PubMed

    Shamsipur, Mojtaba; Asgari, Mehdi; Maragheh, Mohammad Ghannadi; Moosavi-Movahedi, Ali Akbar

    2012-02-01

    A robust and effective nanocomposite film-glassy carbon modified electrode based on multi-walled carbon nanotubes and a room temperature ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate was prepared by a layer-by-layer self-assembly method. The fabricated modified electrode was used as a novel impedimetric catalase nanobiosensor for the determination of H(2)O(2). Direct electron transfer and electrocatalysis of catalase were fully investigated. The results suggested that catalase could be firmly adsorbed at the modified electrode. A pair of quasi-reversible redox peaks of catalase was observed in a 0.20 M degassed phosphate buffer solution of pH 7.0. The nanocomposite film showed a pronounced increase in direct electron transfer between catalase and the electrode. The immobilized catalase exhibited an excellent electrocatalytic activity towards the reduction of H(2)O(2). The electrochemical impedance spectroscopy measurements revealed that the charge transfer resistance decreases significantly after enzymatic reaction with hydrogen peroxide, so that the prepared modified electrode can be used for the detection of ultra traces of H(2)O(2) (5-1700 nM).

  14. Development of Bitter Taste Sensor Using Ionic-Liquid/Polymer Membranes

    NASA Astrophysics Data System (ADS)

    Akutagawa, Nobuyuki; Toida, Jinichi; Amano, Yoshihiko; Ikezaki, Hidekazu; Toko, Kiyoshi; Arikawa, Yukihiko

    A taste sensor is composed of several kinds of lipid/polymer membranes as transducers which convert taste information to electric signal. Thus, the role of membranes is very important to detect various taste components. In this paper, we developed novel membranes which specifically respond to quinine that is typical bitter substances. These membranes were composed of hydrophobic ionic liquid such as N, N, N-trimethyl-N-propylammonium bis(trifluoromethansulfonyl)imide, 1-butyl-3-methylimidazolium hexafluorophosphate and 1-butylpyridinium hexafluorophosphate, a plasticizer, 2-nitrophenyl octyl ether and a polymer, polyvinyl chloride. In addition to quinine, they also showed response to both several kinds of alkaloids such as caffeine and strychnine, and non-alkaloid such as phenylthiocarbamide. The order of these responses was equal to that of the tongue glossopharyngeal nerve of flog. Furthermore, there were the other alkaloids which response to these membranes. Especially in these alkaloids, they showed high response to denatonium benzoate and berberin chloride which have a strong bitter taste.

  15. Toxicity of two imidazolium ionic liquids, [bmim][BF4] and [omim][BF4], to standard aquatic test organisms: Role of acetone in the induced toxicity.

    PubMed

    Tsarpali, Vasiliki; Dailianis, Stefanos

    2015-07-01

    The main goal of this study was to investigate the toxicity of the imidazolium-based ionic liquids (ILs), [bmim][BF4] (1-butyl-3-methylimidazolium tetrafluoroborate) and [omim][BF4] (1-octyl-3-methylimidazolium tetrafluoroborate), in battery of standard aquatic toxicity test organisms. Specifically, exposure of the algae Scenedesmus rubescens, crustaceans Thamnocephalus platyurus and Artemia franciscana, rotifers Brachionus calyciflorus and Brachionus plicatilis and bivalve Mytilus galloprovincialis to different concentrations of [bmim][BF4], [omim][BF4] and/or a binary mixture of [bmim][BF4]-[omim][BF4] (1:1) with or without acetone (carrier solvent), revealed that solvent can differentially mediate ILs' toxic profile. Acetone's ability to differentially affect ILs' cation's alkyl chain length, as well as the hydrolysis of [BF4(-)] anions was evident. Given that the toxic potency of the tested ILs seemed to be equal or even higher (in some cases) than those of conventional organic solvents, the present study revealed that the characterization of imidazolium-based ILs as "green solvents" should not be generalized, at least in case of their natural occurrence in mixtures with organic solvents, such as acetone.

  16. Enhanced Horizontal Transfer of Antibiotic Resistance Genes in Freshwater Microcosms Induced by an Ionic Liquid

    PubMed Central

    Wang, Qing; Mao, Daqing; Mu, Quanhua; Luo, Yi

    2015-01-01

    The spread and propagation of antibiotic resistance genes (ARGs) is a worldwide public health concern. Ionic liquids (ILs), considered as “environmentally friendly” replacements for industrial organic solvents, have been widely applied in modern industry. However, few data have been collected regarding the potential ecological and environmental risks of ILs, which are important for preparing for their potential discharge into the environment. In this paper, the IL 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIm][PF6]) (0.001-5.0 g/L) was tested for its effects on facilitating ARGs horizontal transfer mediated by plasmid RP4 in freshwater microcosms. In the horizontal transfer microcosms, the transfer frequency of plasmid RP4 was significantly enhanced (60-fold higher than untreated groups) by the IL [BMIm][PF6] (1.0 g/L). Meanwhile, two strains of opportunistic pathogen Acinetobacter spp. and Salmonella spp. were isolated among the transconjugants, illustrating plasmid RP4 mediated horizontal transfer of ARGs occurred in pathogen. This could increase the risk of ARGs dissemination to human pathogens and pose great threat to public health. The cause that [BMIm[PF6] enhanced the transfer frequency of plasmid RP4 was proposed by suppressed cell membrane barrier and enhanced cell membrane permeability, which was evidenced by flow cytometry (FCM). This is the first report that some ILs facilitate horizontal transfer of plasmid RP4 which is widely distributed in the environment and thus add the adverse effects of the environmental risk of ILs. PMID:25951456

  17. Surface study of metal-containing ionic liquids by means of photoemission and absorption spectroscopies

    NASA Astrophysics Data System (ADS)

    Caporali, Stefano; Pedio, Maddalena; Chiappe, Cinzia; Pomelli, Christian S.; Acres, Robert G.; Bardi, Ugo

    2016-06-01

    The vacuum/liquid interface of different ionic liquids obtained by dissolving bistriflimide salts of Ag, Al, Cu, Ni, and Zn in 1-butyl-3-methylimidazolium bistriflimide ([bmim][Tf2N]) was investigated under vacuum using AR-XPS and NEXAFS. The XPS spectra show chemical shifts of the nitrogen of the bistriflimide anion as a function of the metal type, indicating different strength of the coordination bonds. In silver bearing ILs, silver ions were found to be only weakly coordinated. On the contrary, Ni, Cu, Zn, and especially Al exhibit large chemical shifts attributable to strong interaction with the bistriflimide ions. The outermost surface was enriched with or depleted of metal ions as a function of the nature of the metals. Nickel and zinc tend to slightly concentrate at the surface while copper, silver, and especially aluminum are depleted at the surface. We also observed that the aliphatic alkyl chains of the cations tend to protrude outside the surface in all systems studied. However, the presence of metals generally increases the amount of bistriflimide at the vacuum/liquid interface.

  18. Association structures of ionic liquid/DMSO mixtures studied by high-pressure infrared spectroscopy

    NASA Astrophysics Data System (ADS)

    Jiang, Jyh-Chiang; Lin, Kuan-Hung; Li, Sz-Chi; Shih, Pao-Ming; Hung, Kai-Chan; Lin, Sheng Hsien; Chang, Hai-Chou

    2011-01-01

    Using high-pressure infrared methods, we have investigated close interactions of charge-enhanced C-H-O type in ionic liquid/dimethyl sulfoxide (DMSO) mixtures. The solvation and association of the 1-butyl-3-methylimidazolium tetrafluoroborate (BMI^ + BF_4^ - ) and 1-butyl-2,3-dimethylimidazolium tetrafluoroborate (BMM^ + BF_4^ - ) in DMSO-d6 were examined by analysis of C-H spectral features. Based on our concentration-dependent results, the imidazolium C-H groups are more sensitive sites for C-H-O than the alkyl C-H groups and the dominant imidazolium C-H species in dilute ionic liquid/DMSO-d6 should be assigned to the isolated (or dissociated) structures. As the dilute mixtures were compressed by high pressures, the loss in intensity of the bands attributed to the isolated structures was observed. In other words, high pressure can be used to perturb the association-dissociation equilibrium in the polar region. This result is remarkably different from what is revealed for the imidazolium C-H in the BMM^ + BF_4^ - /D2O mixtures. DFT-calculations are in agreement with our experimental results indicating that C4-H-O and C5-H-O interactions seem to play non-negligible roles for BMM^ + BF_4^ - /DMSO mixtures.

  19. Catalysis of rice straw hydrolysis by the combination of immobilized cellulase from Aspergillus niger on β-cyclodextrin-Fe3O4 nanoparticles and ionic liquid.

    PubMed

    Huang, Po-Jung; Chang, Ken-Lin; Hsieh, Jung-Feng; Chen, Shui-Tein

    2015-01-01

    Cellulase from Aspergillus niger was immobilized onto β-cyclodextrin-conjugated magnetic particles by silanization and reductive amidation. The immobilized cellulase gained supermagnetism due to the magnetic nanoparticles. Ninety percent of cellulase was immobilized, but the activity of immobilized cellulase decreased by 10%. In this study, ionic liquid (1-butyl-3-methylimidazolium chloride) was introduced into the hydrolytic process because the original reaction was a solid-solid reaction. The activity of immobilized cellulase was improved from 54.87 to 59.11 U g immobilized cellulase(-1) at an ionic liquid concentration of 200 mM. Using immobilized cellulase and ionic liquid in the hydrolysis of rice straw, the initial reaction rate was increased from 1.629 to 2.739 g h(-1) L(-1). One of the advantages of immobilized cellulase is high reusability--it was usable for a total of 16 times in this study. Compared with free cellulase, magnetized cellulase can be recycled by magnetic field and the activity of immobilized cellulase was shown to remain at 85% of free cellulase without denaturation under a high concentration of glucose (15 g L(-1)). Therefore, immobilized cellulase can hydrolyze rice straw continuously compared with free cellulase. The amount of harvested glucose can be up to twentyfold higher than that from the hydrolysis by free cellulase.

  20. Synthesis, micellization behavior and alcohol induced amphipathic cellulose film of cellulose-based amphiphilic surfactant

    NASA Astrophysics Data System (ADS)

    Yang, Fang; Liu, Ya-nan; Yu, Jian-ling; Li, Hai-peng; Li, Gang

    2015-08-01

    This paper presented a novel preparation method of the cellulose-based amphiphilic surfactant, and the surfactant was used to prepare amphipathic cellulose membrane. The native cotton cellulose was tailored to cellulose segments in ionic liquid 1-butyl-3-methylimidazolium chloride. Then, the hydrophobic and hydrophilic modification of cellulose segments were carried out by esterification and graft polymerization of the ɛ-caprolactone (ɛ-CL) monomer onto the hydroxyl group of cellulose as well as sulphonation with sulfamic acid. The amphipathic cellulose membrane was made by cellulose-based amphiphilic surfactant cross-linking with glutaraldehyde. The molecular structure of amphipathic cellulose surfactant was confirmed by FT-IR, and its surface active properties were investigated by Wilhelmy plate method and Steady-state fluorescence probe method, respectively. Experimental results showed that cellulose-based amphiphilic surfactant caused low interfacial tension of 48.62 mN/m and its critical micelle concentration (cmc) value was 0.65 wt% when the grafting ratio of cellulose-g-PCL (poly-caprolactone) was 25.40%. The contact angle between a droplet of water and the surface of membrane was 90.84o, and the surface free energy of the alcohol induced cellulose membrane was 15.7 mJ/m2. This study may help increase using natural and biodegradable surface-activity materials with improved properties as surfactants.

  1. Field Effect Transistors Using Atomically Thin Layers of Copper Indium Selenide (CuInSe)

    NASA Astrophysics Data System (ADS)

    Patil, Prasanna; Ghosh, Sujoy; Wasala, Milinda; Lei, Sidong; Vajtai, Robert; Ajayan, Pulickel; Talapatra, Saikat

    We will report fabrication of field-effect transistors (FETs) using few-layers of Copper Indium Selenide (CuInSe) flakes exfoliated from crystals grown using chemical vapor transport technique. Our transport measurements indicate n-type FET with electron mobility µ ~ 3 cm2 V-1 s-1 at room temperature when Silicon dioxide (SiO2) is used as a back gate. Mobility can be further increased significantly when ionic liquid 1-Butyl-3-methylimidazolium hexafluorophosphate (BMIM-PF6) is used as top gate. Similarly subthreshold swing can be further improved from 103 V/dec to 0.55 V/dec by using ionic liquid as a top gate. We also found ON/OFF ratio of ~ 102 for both top and back gate. Comparison between ionic liquid top gate and SiO2 back gate will be presented and discussed. This work is supported by the U.S. Army Research Office through a MURI Grant # W911NF-11-1-0362.

  2. Solubility and solvation of monosaccharides in ionic liquids.

    PubMed

    Teles, Ana Rita R; Dinis, Teresa B V; Capela, Emanuel V; Santos, Luís M N B F; Pinho, Simão P; Freire, Mara G; Coutinho, João A P

    2016-07-20

    Herein, solubility experimental data for six monosaccharides, viz.d-(+)-glucose, d-(+)-mannose, d-(-)-fructose, d-(+)-galactose, d-(+)-xylose and l-(+)-arabinose, in four ionic liquids (ILs), at temperatures ranging from 288.2 to 348.2 K, were obtained aimed at gathering a better understanding of their solvation ability and molecular-level mechanisms which rule the dissolution process. To ascertain the chemical features that enhance the solubility of monosaccharides, ILs composed of dialkylimidazolium or tetraalkylphosphonium cations combined with the dicyanamide, dimethylphosphate or chloride anions were investigated. It was found that the ranking of the solubility of monosaccharides depends on the IL; yet, d-(+)-xylose is always the most soluble while d-(-)-fructose is the least soluble monosaccharide. The results obtained show that both the IL cation and the anion play a major role in the solubility of monosaccharides. Finally, from the determination of the respective thermodynamic properties of solution, it was found that enthalpic contributions are dominant in the solubilization process. However, the observed differences in the solubilities of monosaccharides in 1-butyl-3-methylimidazolium dicyanamide are ruled by a change in the entropy of solution. PMID:27380720

  3. Development of an ionic liquid-based microwave-assisted method for simultaneous extraction and distillation for determination of proanthocyanidins and essential oil in Cortex cinnamomi.

    PubMed

    Liu, Ye; Yang, Lei; Zu, Yuangang; Zhao, Chunjian; Zhang, Lin; Zhang, Ying; Zhang, Zhonghua; Wang, Wenjie

    2012-12-15

    Cortex cinnamomi is associated with many health benefits and is used in the food and pharmaceutical industries. In this study, an efficient ionic liquid-based microwave-assisted simultaneous extraction and distillation (ILMSED) technique was used to extract cassia oil and proanthocyanidins from Cortex cinnamomi; these were quantified by gas chromatography/mass spectrometry (GC-MS) and the vanillin-HCl colorimetric method, respectively. 0.5M 1-butyl-3-methylimidazolium bromide ionic liquid was selected as solvent. The optimum parameters of dealing with 20.0 g sample were 230 W microwave irradiation power, 15 min microwave extraction time and 10 liquid-solid ratio. The yields of essential oil and proanthocyanidins were 1.24 ± 0.04% and 4.58 ± 0.21% under the optimum conditions. The composition of the essential oil was analysed by GC-MS. Using the ILMSED method, the energy consumption was reduced and the extraction yields were improved. The proposed method was validated using stability, repeatability, and recovery experiments. The results indicated that the developed ILMSED method provided a good alternative for the extraction of both the essential oil and proanthocyanidins from Cortex cinnamomi.

  4. Effect of water on structure and dynamics of [BMIM][PF6] ionic liquid: An all-atom molecular dynamics simulation investigation.

    PubMed

    Sharma, Anirban; Ghorai, Pradip Kr

    2016-03-21

    Composition dependent structural and dynamical properties of aqueous hydrophobic 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]) ionic liquid (IL) have been investigated by using all-atom molecular dynamics simulation. We observe that addition of water does not increase significant number of dissociated ions in the solution over the pure state. As a consequence, self-diffusion coefficient of the cation and anion is comparable to each other at all water concentration similar to that is observed for the pure state. Voronoi polyhedra analysis exhibits strong dependence on the local environment of IL concentration. Void and neck distributions in Voronoi tessellation are approximately Gaussian for pure IL but upon subsequent addition of water, we observe deviation from the Gaussian behaviour with an asymmetric broadening with long tail of exponential decay at large void radius, particularly at higher water concentrations. The increase in void space and neck size at higher water concentration facilitates ionic motion, thus, decreasing dynamical heterogeneity and IL reorientation time and increases self-diffusion coefficient significantly.

  5. Unique role of hydrophilic ionic liquid in modifying properties of aqueous Triton X-100

    NASA Astrophysics Data System (ADS)

    Behera, Kamalakanta; Pandey, Mrituanjay D.; Porel, Mintu; Pandey, Siddharth

    2007-11-01

    Modification of important physicochemical properties of aqueous surfactant solutions can be achieved by addition of environmentally benign room temperature ionic liquids (ILs). While low aqueous solubility of ``hydrophobic'' ILs limits the amount of IL that may be added to achieve desired changes in the physicochemical properties, hydrophilic ILs do not have such restrictions associated to them. Alterations in the key physicochemical properties of aqueous solutions of a common nonionic surfactant Triton X-100 (TX100) on addition of up to 30 wt % hydrophilic IL 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]) are reported. The presence of micellar aggregates in as high as 30 wt % [bmim][BF4]-added aqueous TX100 solutions is established by dynamic light scattering and fluorescence probe behavior. Increasing the concentration of [bmim][BF4] results in decrease in average micellar size and aggregation number and increase in critical micelle concentration, indicating an overall unfavorable aggregation process. Increase in the dipolarity and the microfluidity of the probe cybotactic region within the palisade layer of the micellar phase upon [bmim][BF4] addition implies increased water penetration and the possibility of TX100-[bmim][BF4] interactions. While the changes in some of the physicochemical properties indicate the role of [bmim][BF4] to be similar to a cosurfactant, the IL acts like a cosolvent as far as changes in other properties are concerned. Effectiveness of IL [bmim][BF4] in modifying physicochemical properties of aqueous TX100 is demonstrated.

  6. Synthesis, micellization behavior and alcohol induced amphipathic cellulose film of cellulose-based amphiphilic surfactant

    NASA Astrophysics Data System (ADS)

    Yang, Fang; Liu, Ya-nan; Yu, Jian-ling; Li, Hai-peng; Li, Gang

    2015-08-01

    This paper presented a novel preparation method of the cellulose-based amphiphilic surfactant, and the surfactant was used to prepare amphipathic cellulose membrane. The native cotton cellulose was tailored to cellulose segments in ionic liquid 1-butyl-3-methylimidazolium chloride. Then, the hydrophobic and hydrophilic modification of cellulose segments were carried out by esterification and graft polymerization of the ɛ-caprolactone (ɛ-CL) monomer onto the hydroxyl group of cellulose as well as sulphonation with sulfamic acid. The amphipathic cellulose membrane was made by cellulose-based amphiphilic surfactant cross-linking with glutaraldehyde. The molecular structure of amphipathic cellulose surfactant was confirmed by FT-IR, and its surface active properties were investigated by Wilhelmy plate method and Steady-state fluorescence probe method, respectively. Experimental results showed that cellulose-based amphiphilic surfactant caused low interfacial tension of 48.62 mN/m and its critical micelle concentration (cmc) value was 0.65 wt% when the grafting ratio of cellulose-g-PCL (poly-caprolactone) was 25.40%. The contact angle between a droplet of water and the surface of membrane was 90.84o, and the surface free energy of the alcohol induced cellulose membrane was 15.7 mJ/m2. This study may help increase using natural and biodegradable surface-activity materials with improved properties as surfactants.

  7. Theoretical Elucidation of Glucose Dehydration to 5-Hydroxymethylfurfural Catalyzed by a SO3H-Functionalized Ionic Liquid.

    PubMed

    Li, Jingjing; Li, Jinghua; Zhang, Dongju; Liu, Chengbu

    2015-10-22

    While the catalytic conversion of glucose to 5-hydroxymethyl furfural (HMF) catalyzed by SO3H-functioned ionic liquids (ILs) has been achieved successfully, the relevant molecular mechanism is still not understood well. Choosing 1-butyl-3-methylimidazolium chloride [C4SO3HmimCl] as a representative of SO3H-functioned IL, this work presents a density functional theory (DFT) study on the catalytic mechanism for conversion of glucose into HMF. It is found that the conversion may proceed via two potential pathways and that throughout most of elementary steps, the cation of the IL plays a substantial role, functioning as a proton shuttle to promote the reaction. The chloride anion interacts with the substrate and the acidic proton in the imidazolium ring via H-bonding, as well as provides a polar environment together with the imidazolium cation to stabilize intermediates and transition states. The calculated overall barriers of the catalytic conversion along two potential pathways are 32.9 and 31.0 kcal/mol, respectively, which are compatible with the observed catalytic performance of the IL under mild conditions (100 °C). The present results provide help for rationalizing the effective conversion of glucose to HMF catalyzed by SO3H-functionalized ILs and for designing IL catalysts used in biomass conversion chemistry. PMID:26434955

  8. Three-phase catalytic system of H2O, ionic liquid, and VOPO4-SiO2 solid acid for conversion of fructose to 5-hydroxymethylfurfural.

    PubMed

    Tian, Chengcheng; Zhu, Xiang; Chai, Song-Hai; Wu, Zili; Binder, Andrew; Brown, Suree; Li, Lin; Luo, Huimin; Guo, Yanglong; Dai, Sheng

    2014-06-01

    Efficient transformation of biomass-derived feedstocks to chemicals and fuels remains a daunting challenge in utilizing biomass as alternatives to fossil resources. A three-phase catalytic system, consisting of an aqueous phase, a hydrophobic ionic-liquid phase, and a solid-acid catalyst phase of nanostructured vanadium phosphate and mesostructured cellular foam (VPO-MCF), is developed for efficient conversion of biomass-derived fructose to 5-hydroxymethylfurfural (HMF). HMF is a promising, versatile building block for production of value-added chemicals and transportation fuels. The essence of this three-phase system lies in enabling the isolation of the solid-acid catalyst from the aqueous phase and regulation of its local environment by using a hydrophobic ionic liquid, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([BMIM][Tf2N]). This system significantly inhibits the side reactions of HMF with H2O and leads to 91 mol % selectivity to HMF at 89 % of fructose conversion. The unique three-phase catalytic system opens up an alternative avenue for making solid-acid catalyst systems with controlled and locally regulated microenvironment near catalytically active sites by using a hydrophobic ionic liquid. PMID:24729382

  9. Hydrolysis of cellulose catalyzed by novel acidic ionic liquids.

    PubMed

    Zhuo, Kelei; Du, Quanzhou; Bai, Guangyue; Wang, Congyue; Chen, Yujuan; Wang, Jianji

    2015-01-22

    The conversion of cellulosic biomass directly into valuable chemicals becomes a hot subject. Six novel acidic ionic liquids (ILs) based on 2-phenyl-2-imidazoline were synthesized and characterized by UV-VIS, TGA, and NMR. The novel acidic ionic liquids were investigated as catalysts for the hydrolysis of cellulose in 1-butyl-3-methylimidazolium chloride ([Bmim]Cl). The acidic ionic liquids with anions HSO4(-) and Cl(-) showed better catalytic performance for the hydrolysis of cellulose than those with H2PO4(-). The temperature and dosage of water affect significantly the yield of total reducing sugar (TRS). When the hydrolysis of cellulose was catalyzed by 1-propyl sulfonic acid-2-phenyl imidazoline hydrogensulfate (IL-1) and the dosage of water was 0.2g, the TRS yield was up to 85.1% within 60 min at 100°C. These new acidic ionic liquids catalysts are expected to have a wide application in the conversion of cellulose into valuable chemicals. PMID:25439867

  10. Catalytic conversion of carbohydrates into 5-hydroxymethylfurfural over cellulose-derived carbonaceous catalyst in ionic liquid.

    PubMed

    Hu, Lei; Zhao, Geng; Tang, Xing; Wu, Zhen; Xu, Jiaxing; Lin, Lu; Liu, Shijie

    2013-11-01

    Three environmental-benign and low-cost carbon-based solid acid catalysts containing -SO3H, -COOH and phenolic -OH groups were prepared and used for the conversion of glucose into 5-hydroxymethylfurfural (HMF) in ionic liquid 1-butyl-3-methylimidazolium chloride ([BMIM]Cl). The results demonstrated that cellulose-derived carbonaceous catalyst (CCC) possessed the highest catalytic activity, which resulted in 46.4% HMF yield at 160°C for only 15 min. In addition, the reaction kinetics for the conversion of glucose into HMF over CCC was fitted with the first-order rate equation. The slightly-deactivated CCC after four successive reaction runs could be easily regenerated by a simple carbonization and sulfonation process. More gratifyingly, the combination of CCC and [BMIM]Cl were confirmed to be suitable for converting other carbohydrates such as fructose, sucrose, maltose, cellobiose, starch and cellulose into HMF. Particularly, a plausible mechanism involving hydrolysis, isomerization and dehydration for the conversion of carbohydrates into HMF was also proposed. PMID:24090810

  11. Conversion of xylan, d-xylose and lignocellulosic biomass into furfural using AlCl3 as catalyst in ionic liquid.

    PubMed

    Zhang, Luxin; Yu, Hongbing; Wang, Pan; Dong, Heng; Peng, Xinhong

    2013-02-01

    In order to define a new green catalytic pathway for the production of furfural, the catalyzed conversion of xylan into furfural in 1-butyl-3-methylimidazolium chloride was studied by using mineral acids and metal chlorides as catalysts under microwave irradiation. Amongst these catalysts, AlCl(3) resulted in the highest furfural yield of 84.8% at 170°C for 10s. The effect of AlCl(3) on the conversion efficiency of d-xylose and untreated lignocellulosic biomass was also investigated, the yields of furfural from corncob, grass and pine wood catalyzed by AlCl(3) in [BMIM]Cl were in the range of 16-33%. [BMIM]Cl and AlCl(3) could be recycled for four runs with stable catalytic activity. AlCl(3) is less corrosive than mineral acids, and the use of ionic liquid as reaction medium will no longer generate toxic wastewater, thus this reaction system is more ecologically viable. PMID:23306118

  12. "One-step production of biodiesel from Jatropha oil with high-acid value in ionic liquids" [Bioresour. Technol. 102 (11) (2011)].

    PubMed

    Guo, Feng; Fang, Zhen; Tian, Xiao-fei; Long, Yun-Duo; Jiang, Li-Qun

    2013-07-01

    Catalytic conversion of un-pretreated Jatropha oil with high-acid value (13.8 mg KOH/g) to biodiesel was studied in ionic liquids (ILs) with metal chlorides. Several commercial ILs were used to catalyze the esterification of oleic acid. It was found that 1-butyl-3-methylimidazolium tosylate {[BMIm][TS]} had high catalytic activity with 93% esterification rate for oleic acid at 140 °C but only 63.7% Jatropha biodiesel yield at 200 °C. When ZnCl2 was added to [BMIm][TS], a maximum Jatropha biodiesel yield of 92.5% was achieved at 180 °C. Addition of metal ions supplied Lewis acidic sites in ILs promoted both esterification and transestrification reactions. It was also found that the transition metal ions performed higher catalytic activity in transestrification than the ions of Group A. Mixture of [BMIm][TS] and ZnCl2 was easily separated from products for reuse to avoid producing pollutants. PMID:23908993

  13. Conversion of fructose and glucose into 5-hydroxymethylfurfural with lignin-derived carbonaceous catalyst under microwave irradiation in dimethyl sulfoxide-ionic liquid mixtures.

    PubMed

    Guo, Feng; Fang, Zhen; Zhou, Tie-Jun

    2012-05-01

    5-Hydroxymethylfurfural (5-HMF) was successfully produced by the dehydration of fructose and glucose using lignin-derived solid acid catalyst in DMSO-[BMIM][Cl] (dimethyl sulfoxide and 1-butyl-3-methylimidazolium chloride) mixtures. Six solid acid catalysts were synthesized by carbonization and sulfonation of raw biomass materials, i.e., glucose, fructose, cellulose, lignin, bamboo and Jatropha hulls. It was found that lignin-derived solid acid catalyst (LCC) was the most active one in the dehydration of sugars. LCC coupled with microwave irradiation was used for the 5-HMF production, 84% 5-HMF yield with 98% fructose conversion rate was achieved at 110°C for 10 min. Furthermore, 99% glucose was converted with 68% 5-HMF yield under severer condition (160°C for 50 min). LCC was recycled for five times, 5-HMF yield declined only 7%. Use of LCC combined with DMSO-[BMIM][Cl] solution and microwave irradiation is a novel method for the effective production of 5-HMF. PMID:22429401

  14. One-step production of biodiesel from Jatropha oil with high-acid value in ionic liquids.

    PubMed

    Guo, Feng; Fang, Zhen; Tian, Xiao-Fei; Long, Yun-Duo; Jiang, Li-Qun

    2011-06-01

    Catalytic conversion of un-pretreated Jatropha oil with high-acid value (13.8 mg KOH/g) to biodiesel was studied in ionic liquids (ILs) with metal chlorides. Several commercial ILs were used to catalyze the esterification of oleic acid. It was found that 1-butyl-3-methylimidazolium tosylate ([BMIm][CH(3)SO(3)]; a Brønsted acidic IL) had the highest catalytic activity with 93% esterification rate for oleic acid at 140°C but only 12% biodiesel yield at 120°C. When FeCl(3) was added to [BMIm][CH(3)SO(3)], a maximum biodiesel yield of 99.7% was achieved at 120°C. Because metal ions in ILs supplied Lewis acidic sites, and more of the sites could be provided by trivalent metallic ions than those of bivalent ones. It was also found that the catalytic activity with bivalent metallic ions increased with atomic radius. Mixture of [BMIm][CH(3)SO(3)] and FeCl(3) was easily separated from products for reuse to avoid producing pollutants. PMID:21420854

  15. Influence of the molecular-oriented structure of ionic liquids on the crystallinity of aluminum hydroxide prepared by a sol-gel process in ionic liquids.

    PubMed

    Kinoshita, K; Yanagimoto, H; Suzuki, T; Minami, H

    2015-07-28

    The influence of the structure of ionic liquids on the crystallinity of aluminum hydroxide (Al(OH)3) prepared by a sol-gel process with aluminum isopropoxide (Al(OPr(i))3) in imidazolium-based ionic liquids was investigated. When Al(OH)3 was prepared in ionic liquids having long alkyl chains, such as 1-butyl-3-methylimidazolium salts and 1-methyl-3-octylimidazolium salts, highly crystalline products were obtained. In contrast, Al(OH)3 obtained using the 1-ethyl-3-methylimidazolium salt was an amorphous material, indicating that hydrophobic interaction of the alkyl tail of the imidazolium cation of the ionic liquid strongly affects the crystallinity of sol-gel products and the local structure of the ionic liquid. Moreover, the crystallinity of Al(OH)3 prepared in ionic liquids increased relative to the amount of additional water (ionic liquid/water = 1.28/2.0-3.5/0.2, w/w). In the case of addition of a small amount of water (ionic liquid/water = 3.5/0.2, w/w), the product was amorphous. These results implied that the presence of an ionic liquid and a sufficient amount of water was crucial for the successful synthesis of sol-gel products with high crystallinity. (1)H NMR analyses revealed a shift of the peak associated with the imidazolium cation upon addition of water, which suggested that the molecular orientation of the ionic liquid was similar to that of a micelle. PMID:26118363

  16. Nonaborane and decaborane cluster anions can enhance the ignition delay in hypergolic ionic liquids and induce hypergolicity in molecular solvents.

    PubMed

    McCrary, Parker D; Barber, Patrick S; Kelley, Steven P; Rogers, Robin D

    2014-05-01

    The dissolution of nido-decaborane, B10H14, in ionic liquids that are hypergolic (fuels that spontaneously ignite upon contact with an appropriate oxidizer), 1-butyl-3-methylimidazolium dicyanamide, 1-methyl-4-amino-1,2,4-triazolium dicyanamide, and 1-allyl-3-methylimidazolium dicyanamide, led to the in situ generation of a nonaborane cluster anion, [B9H14](-), and reductions in ignition delays for the ionic liquids suggesting salts of borane anions could enhance hypergolic properties of ionic liquids. To explore these results, four salts based on [B10H13](-) and [B9H14](-), triethylammonium nido-decaborane, tetraethylammonium nido-decaborane, 1-ethyl-3-methylimidazolium arachno-nonaborane, and N-butyl-N-methyl-pyrrolidinium arachano-nonaborane were synthesized from nido-decaborane by reaction of triethylamine or tetraethylammonium hydroxide with nido-decaborane in the case of salts containing the decaborane anion or via metathesis reactions between sodium nonaborane (Na[B9H14]) and the corresponding organic chloride in the case of the salts containing the nonaborane anion. These borane cluster anion salts form stable solutions in some combustible polar aprotic solvents such as tetrahydrofuran and ethyl acetate and trigger hypergolic reactivity of these solutions. Solutions of these salts in polar protic solvents are not hypergolic. PMID:24716643

  17. Comparison of different ionic liquids pretreatment for corn stover enzymatic saccharification.

    PubMed

    Mood, Sohrab Haghighi; Golfeshan, Amir Hossein; Tabatabaei, Meisam; Abbasalizadeh, Saeed; Ardjmand, Mehdi; Jouzani, Gholamreza Salehi

    2014-01-01

    Recently, application of ionic liquids (ILs) has received much attention due to their special solvency properties as a promising method of pretreatment for lignocellulosic biomass. Easy recovery of ionic liquids, chemical stability, temperature stability, nonflammability, low vapor pressure, and wide liquidus range are among those unique properties. These solvents are also known as green solvents due to their low vapor pressure. The present study was set to compare the effect of five different ILs, namely, 1-ethyl-3-methylimidazolium acetate ([EMIM][Ac]), 1-butyl-3-methylimidazolium chloride ([BMIM][Cl]), 1-ethyl-3-methyl imidazolium diethyl phosphate ([EMIM][DEP]), 1-allyl-3-methylimidazolium chloride ([AMIM][Cl]), and 1-ethyl-3-methylimidazolium-hydrogen sulfate ([EMIM][HSO₄]), on corn stover in a bioethanol production process. The performance of ILs was evaluated based on the change observed in chemical structure, crystallinity index, cellulose digestibility, and glucose release. Overall, [EMIM][Ac]-pretreated corn stover led to significantly higher saccharification, with cellulose digestibility reaching 69% after 72 hr, whereas digestibility of untreated barley straw was measured at only 21%. PMID:24397717

  18. Carbene formation upon reactive dissolution of metal oxides in imidazolium ionic liquids.

    PubMed

    Wellens, Sil; Brooks, Neil R; Thijs, Ben; Meervelt, Luc Van; Binnemans, Koen

    2014-03-01

    Metal oxides were found to dissolve in different imidazolium ionic liquids with a hydrogen atom in the C2 position of the imidazolium ring, but not if a methyl substituent was present in the C2 position. The crystal structure of the product that crystallised from an ionic liquid containing dissolved silver(i) oxide showed that this was a silver(i) carbene complex. The presence of carbenes in solution was proven by (13)C NMR spectroscopy and the reactions were also monitored by Raman spectroscopy. The dissolution of other metal oxides, namely copper(ii) oxide, zinc(ii) oxide and nickel(ii) oxide, was also studied in imidazolium ionic liquids and it was found that stable zinc(ii) carbenes were formed in solution, but these did not crystallise under the given experimental conditions. A crystalline nickel(ii) carbene complex could be obtained from a solution of nickel(ii) chloride dissolved in a mixture of 1-butyl-3-methylimidazolium and 1-ethyl-3-methylimidazolium acetate. PMID:24390601

  19. Topochemical pretreatment of wood biomass to enhance enzymatic hydrolysis of polysaccharides to sugars.

    PubMed

    Mou, Hong-Yan; Orblin, Elina; Kruus, Kristiina; Fardim, Pedro

    2013-08-01

    The surface chemistry of milled birch and pine wood pretreated by ionic liquid, hydrothermal and hydrotropic methods, followed by enzymatic hydrolysis was studied in this work. Surface coverage by lignin was measured by X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS) was used to describe the surface chemical composition after pretreatment in detail, and the morphology after pretreatment was investigated by FE-SEM. Ionic liquid (1-ethyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium chloride) pretreatment at room temperature made the samples swell but did not dissolve the wood. Comparing the surface coverage by lignin, both in the case of birch and pine wood, hydrotropic worked best to remove the lignin hampering enzymatic hydrolysis. ToF-SIMS supported this finding, and showed that in birch, the carbohydrates were degraded more than in pine after hydrotropic pretreatment. The glucose yield of birch was improved by hydrotropic pretreatment from 5.1% to 83.9%, more significantly than in case of pine. PMID:23774220

  20. SEM Observation of Hydrous Superabsorbent Polymer Pretreated with Room-Temperature Ionic Liquids

    PubMed Central

    Tsuda, Tetsuya; Mochizuki, Eiko; Kishida, Shoko; Iwasaki, Kazuki; Tsunashima, Katsuhiko; Kuwabata, Susumu

    2014-01-01

    Room-temperature ionic liquid (RTIL), which is a liquid salt at or below room temperature, shows peculiar physicochemical properties such as negligible vapor pressure and relatively-high ionic conductivity. In this investigation, we used six types of RTILs as a liquid material in the pretreatment process for scanning electron microscope (SEM) observation of hydrous superabsorbent polymer (SAP) particles. Very clear SEM images of the hydrous SAP particles were obtained if the neat RTILs were used for the pretreatment process. Of them, tri-n-butylmethylphosphonium dimethylphosphate ([P4, 4, 4, 1][DMP]) provided the best result. On the other hand, the surface morphology of the hydrous SAP particles pretreated with 1-ethyl-3-methylimidazolium tetrafluoroborate ([C2mim][BF4]) and 1-butyl-3-methylimidazolium tetrafluoroborate ([C4mim][BF4]) was damaged. The results of SEM observation and thermogravimetry analysis of the hydrous SAP pretreated with the RTILs strongly suggested that most water in the SAP particles are replaced with RTIL during the pretreatment process. PMID:24621609

  1. Combined effects of raw materials and solvent systems on the preparation and properties of regenerated cellulose fibers.

    PubMed

    Chen, Jinghuan; Guan, Ying; Wang, Kun; Zhang, Xueming; Xu, Feng; Sun, Runcang

    2015-09-01

    To investigate the combined effects of materials and solvents on the preparation, structural and mechanical properties of regenerated cellulose fibers, four cellulosic materials (microcrystalline cellulose, cotton linter pulp, bamboo pulp and bleached softwood sulfite dissolving pulp) and six non-derivative solvents (NaOH/urea aqueous solution, N,N-dimethylacetamide/lithium chloride, N-methyl-morpholine-N-oxide, 1-butyl-3-methylimidazolium chloride, 1-allyl-3-methylimidazolium chloride and 1-ethyl-3-methylimidazolium acetate) were used to prepare fibers with wet spinning method. The results showed that the dissolvability of solvent was the determining factor in cellulose dissolution, and the dissolving time was influenced by the raw materials' properties, such as molecular weight, exposed area and hemicellulose content. The crystallinity and elongation at break of the fibers were almost fixed and not affected by the materials and solvents. However, the tensile strength of the fibers was directly proportional to the molecular weight of the raw materials, and varied with the type of solvents through cellulose degradation. PMID:26005150

  2. Catalysis of Rice Straw Hydrolysis by the Combination of Immobilized Cellulase from Aspergillus niger on β-Cyclodextrin-Fe3O4 Nanoparticles and Ionic Liquid

    PubMed Central

    Huang, Po-Jung; Chang, Ken-Lin; Chen, Shui-Tein

    2015-01-01

    Cellulase from Aspergillus niger was immobilized onto β-cyclodextrin-conjugated magnetic particles by silanization and reductive amidation. The immobilized cellulase gained supermagnetism due to the magnetic nanoparticles. Ninety percent of cellulase was immobilized, but the activity of immobilized cellulase decreased by 10%. In this study, ionic liquid (1-butyl-3-methylimidazolium chloride) was introduced into the hydrolytic process because the original reaction was a solid-solid reaction. The activity of immobilized cellulase was improved from 54.87 to 59.11 U g immobilized cellulase−1 at an ionic liquid concentration of 200 mM. Using immobilized cellulase and ionic liquid in the hydrolysis of rice straw, the initial reaction rate was increased from 1.629 to 2.739 g h−1 L−1. One of the advantages of immobilized cellulase is high reusability—it was usable for a total of 16 times in this study. Compared with free cellulase, magnetized cellulase can be recycled by magnetic field and the activity of immobilized cellulase was shown to remain at 85% of free cellulase without denaturation under a high concentration of glucose (15 g L−1). Therefore, immobilized cellulase can hydrolyze rice straw continuously compared with free cellulase. The amount of harvested glucose can be up to twentyfold higher than that from the hydrolysis by free cellulase. PMID:25874210

  3. Dissolving process of a cellulose bunch in ionic liquids: a molecular dynamics study.

    PubMed

    Li, Yao; Liu, Xiaomin; Zhang, Suojiang; Yao, Yingying; Yao, Xiaoqian; Xu, Junli; Lu, Xingmei

    2015-07-21

    In recent years, a variety of ionic liquids (ILs) were found to be capable of dissolving cellulose and mechanistic studies were also reported. However, there is still a lack of detailed information at the molecular level. Here, long time molecular dynamics simulations of cellulose bunch in 1-ethyl-3-methylimidazolium acetate (EmimAc), 1-ethyl-3-methylimidazolium chloride (EmimCl), 1-butyl-3-methylimidazolium chloride (BmimCl) and water were performed to analyze the inherent interaction and dissolving mechanism. Complete dissolution of the cellulose bunch was observed in EmimAc, while little change took place in EmimCl and BmimCl, and nothing significant happened in water. The deconstruction of the hydrogen bond (H-bond) network in cellulose was found and analyzed quantitatively. The synergistic effect of cations and anions was revealed by analyzing the whole dissolving process. Initially, cations bind to the side face of the cellulose bunch and anions insert into the cellulose strands to form H-bonds with hydroxyl groups. Then cations start to intercalate into cellulose chains due to their strong electrostatic interaction with the entered anions. The H-bonds formed by Cl(-) cannot effectively separate the cellulose chain and that is the reason why EmimCl and BmimCl dissolve cellulose more slowly. These findings deepen people's understanding on how ILs dissolve cellulose and would be helpful for designing new efficient ILs to dissolve cellulose. PMID:26095890

  4. Lyotropic Phase Behavior of Polybutadiene-Poly(ethylene oxide) Diblock Copolymers in Ionic Liquids

    SciTech Connect

    Simone, Peter M.; Lodge, Timothy P.

    2008-08-26

    The lyotropic phase behavior of three poly(1,2-butadiene-b-ethylene oxide) diblock copolymers (PB-PEO) with different monomer volume fractions has been studied in two different ionic liquids, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMI][TFSI]) and 1-butyl-3-methylimidazolium hexafluorophosphate ([BMI][PF{sub 6}]), across the complete concentration range. The ordered microstructures present in the solutions were characterized via small-angle X-ray scattering (SAXS). The phase diagrams for the PB-PEO/ionic liquid solutions include regions corresponding to the classical copolymer microstructures: body-centered-cubic lattices of spheres, hexagonally ordered cylinders, and lamellae. Additionally, the phase diagrams also include wide regions of coexisting microstructures and regions apparently corresponding to a disordered network microstructure. The phase behavior of the PB-PEO copolymers in both ionic liquids was comparable to their previously reported aqueous solution behavior. The temperature dependence of the phase diagrams was very modest, indicative of a highly segregated system. The level of solvent selectivity was also investigated via cryogenic transmission electron microscopy (cryo-TEM) on dilute solutions. On the basis of the morphology of the dilute solution copolymer aggregate structures in the ionic liquid solvents, and on the structural length scales of the concentrated solutions, it was concluded that for PB-PEO [BMI][PF{sub 6}] behaves as a more selective solvent than [EMI][TFSI].

  5. A Comprehensive Study on Lyotropic Liquid-Crystalline Behavior of an Amphiphile in 20 Kinds of Amino Acid Ionic Liquids.

    PubMed

    Fujimura, Kanae; Ichikawa, Takahiro; Yoshio, Masafumi; Kato, Takashi; Ohno, Hiroyuki

    2016-02-18

    We examined the self-organization behavior of a designed amphiphilic molecule in 20 kinds of amino acid ionic liquids composed of 1-butyl-3-methylimidazolium cation and natural amino acid anion ([C4mim][AA]). Addition of [C4mim][AA], regardless of their anion species, to the amphiphile provided homogeneous mixtures showing lyotropic liquid-crystalline (LC) behavior. Upon increasing the component ratio of [C4mim][AA] in the mixtures, a successive change of the mesophase patterns from inverted hexagonal columnar, in some case via bicontinuous cubic, to layered phases was observed. By examining the LC properties at various temperatures and component ratios, we constructed lyotropic LC phase diagrams. Interestingly, the appearance of these phase diagrams is greatly different according to the selection of [AA]. Through comparison, we found that the self-organization behavior of an amphiphile in ionic liquids can be tuned by controlling their ability to form hydrogen-bond, van der Waals, and π-π interactions.

  6. Comparative Investigation of the Ionicity of Aprotic and Protic Ionic Liquids in Molecular Solvents by using Conductometry and NMR Spectroscopy.

    PubMed

    Thawarkar, Sachin; Khupse, Nageshwar D; Kumar, Anil

    2016-04-01

    Electrical conductivity (σ), viscosity (η), and self-diffusion coefficient (D) measurements of binary mixtures of aprotic and protic imidazolium-based ionic liquids with water, dimethyl sulfoxide, and ethylene glycol were measured from 293.15 to 323.15 K. The temperature dependence study reveals typical Arrhenius behavior. The ionicities of aprotic ionic liquids were observed to be higher than those of protic ionic liquids in these solvents. The aprotic ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate, [bmIm][BF4 ], displays 100 % ionicity in both water and ethylene glycol. The protic ionic liquids in both water and ethylene glycol are classed as good ionic candidates, whereas in DMSO they are classed as having a poor ionic nature. The solvation dynamics of the ionic species of the ionic liquids are illustrated on the basis of the (1) H NMR chemical shifts of the ionic liquids. The self-diffusion coefficients D of the cation and anion of [HmIm][CH3 COO] in D2 O and in [D6 ]DMSO are determined by using (1) H nuclei with pulsed field gradient spin-echo NMR spectroscopy.

  7. Influence of the molecular-oriented structure of ionic liquids on the crystallinity of aluminum hydroxide prepared by a sol-gel process in ionic liquids.

    PubMed

    Kinoshita, K; Yanagimoto, H; Suzuki, T; Minami, H

    2015-07-28

    The influence of the structure of ionic liquids on the crystallinity of aluminum hydroxide (Al(OH)3) prepared by a sol-gel process with aluminum isopropoxide (Al(OPr(i))3) in imidazolium-based ionic liquids was investigated. When Al(OH)3 was prepared in ionic liquids having long alkyl chains, such as 1-butyl-3-methylimidazolium salts and 1-methyl-3-octylimidazolium salts, highly crystalline products were obtained. In contrast, Al(OH)3 obtained using the 1-ethyl-3-methylimidazolium salt was an amorphous material, indicating that hydrophobic interaction of the alkyl tail of the imidazolium cation of the ionic liquid strongly affects the crystallinity of sol-gel products and the local structure of the ionic liquid. Moreover, the crystallinity of Al(OH)3 prepared in ionic liquids increased relative to the amount of additional water (ionic liquid/water = 1.28/2.0-3.5/0.2, w/w). In the case of addition of a small amount of water (ionic liquid/water = 3.5/0.2, w/w), the product was amorphous. These results implied that the presence of an ionic liquid and a sufficient amount of water was crucial for the successful synthesis of sol-gel products with high crystallinity. (1)H NMR analyses revealed a shift of the peak associated with the imidazolium cation upon addition of water, which suggested that the molecular orientation of the ionic liquid was similar to that of a micelle.

  8. Theoretical and experimental investigation on the capture of H2S in a series of ionic liquids.

    PubMed

    Zhou, Xinming; Cao, Bobo; Liu, Shuangyue; Sun, Xuejun; Zhu, Xiao; Fu, Hui

    2016-07-01

    H2S absorptions in ionic liquids (ILs), including tetramethyl guanidinelactate (TMGL), 4-bis(2-hydroxypropyl)-1,1,3,3-tetramethyl guanidinium tetrafluoroborate ([TMGHPO2][BF4]) and 1-butyl-3-methylimidazolium cation ([BMIM](+)) with the anions chloride ([Cl](-)), tetrafluoroborate ([BF4](-)), hexafluorophosphate ([PF6](-)), triflate ([TfO](-)), bis-(trifluoromethyl) sulfonylimide ([Tf2N](-)), were studied in experiment and computational methods. [TMGHPO2][BF4] showed the best H2S absorption capacity among the seven ILs. Density functional theory (DFT) calculations were applied to reveal the absorption mechanisms. Interaction energy results were consistent with absorptivities (molar ratio of H2S in IL) measured in experiment. As the best candidate absorbent, [TMGHPO2][BF4] was chosen as an example to characterize the hydrogen bonds and orbital interactions between H2S and [TMGHPO2][BF4] in atoms in molecules (AIM) and natural bond orbital (NBO) methods, respectively. IR spectrums obtained in both experimental and computational method were used to characterize the features of absorption process. The results indicated that H2S was physically absorbed by ILs, in which hydrogen bond was the driving force. PMID:27388120

  9. Self-healing guar gum and guar gum-multiwalled carbon nanotubes nanocomposite gels prepared in an ionic liquid.

    PubMed

    Sharma, Mukesh; Mondal, Dibyendu; Mukesh, Chandrakant; Prasad, Kamalesh

    2013-10-15

    Guar gum is a galactomannan extracted from the seed of the leguminous shrub Cyamopsis tetragonoloba. It was found to form a soft viscoelastic gel in 1-butyl-3-methylimidazolium chloride, an ionic liquid at an optimized concentration of 10%w/v. A nanocomposite gel of the gum with enhanced strength could be prepared with 0.2%w/v of multiwalled carbon nanotubes (MWCNTs) in the ionic liquid. When the gels thus prepared were subjected to surface fractures or bisected completely, they found to self-heal at room temperature without any external interventions. The self-healing process could be repeated several times. These viscoelastic gel systems showed thixotropic nature and recovery of the storage modulus with time for several cycles was observed upon rheological investigations. The interaction took place between ionic liquid, guar gum and MWCNT was studied by SEM, TEM, FT-IR, powder XRD and rheometry. The results suggested that, upon standing at room temperature development of electrostatic interactions and the van der Waals interactions among the ionic liquid molecules facilitated the formation of reversible noncovalent bonds and eventually activated the self-healing in the gel systems through appropriate chain entanglements.

  10. Development of a new green non-dispersive ionic liquid microextraction method in a narrow glass column for determination of cadmium prior to couple with graphite furnace atomic absorption spectrometry.

    PubMed

    Naeemullah; Kazi, Tasneem Gul; Tuzen, Mustafa; Shah, Faheem; Afridi, Hassan Imran; Citak, Demirhan

    2014-02-17

    Easy and innovative non-dispersive ionic liquid based microextraction (NDILME) has been developed for preconcentration of trace level of cadmium (Cd) in aqueous real surface water samples prior to couple with graphite furnace atomic absorption spectrometry (GFAAS). A 200 cm long narrow glass column containing aqueous solution of standard/sample was used to increase phase transfer ratio by providing more contact area between two medium (aqueous and extractive), which drastically improve the recoveries of labile hydrophobic chelate of Cd ammonium pyrrolidinedithiocarbamate (APDC), into ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate [C4mim][PF6]. Different aspect of the desire method have been investigated and optimized. Under the optimized key experimental variables, limit of detection (LOD) and enhancement factor (EF) were achieved to be 0.5 ng L(-1) and 150, respectively. Reliability of the model method was checked by relative standard deviation (%RSD), which was found to be <5%. Validity and accuracy of the developed method was checked by analysis of certified reference water samples (SLRS-4 Riverine water) using standard addition method. Application of the model method was productively performed by analysis of Cd in real surface water samples (tap and sea).

  11. Observation of antibacterial effect of biodegradable polymeric nanoparticles on Staphylococcus epidermidis biofilm using FE-SEM with an ionic liquid.

    PubMed

    Takahashi, Chisato; Ogawa, Noriko; Kawashima, Yoshiaki; Yamamoto, Hiromitsu

    2015-06-01

    We successfully visualized the antibacterial behavior of biodegradable polymeric nanoparticles (NPs) on a biofilm formed by Staphylococcus epidermidis using field emission scanning electron microscopy (FE-SEM). A hydrophilic ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF4]), was applied for observation using FE-SEM. The differences in adherence and penetration behavior of three types of NPs were revealed using this method and confocal laser scanning microscopy. Biodegradable poly(dl-lactide-co-glycolide) (PLGA) NPs were prepared by the emulsion solvent diffusion method. In this study, we treated the biofilm with three PLGA NPs: unmodified PLGA, PLGA modified with chitosan (CS) and clarithromycin (CAM)-loaded + CS-modified PLGA. The viability of S. epidermidis cells treated with PLGA NPs was estimated using the LIVE/DEAD BacLight kit to understand the antibacterial ability of each NP sample in a quantitative way. The results confirmed that CAM-loaded + CS-modified PLGA had high antibacterial ability on the biofilm. This novel observation technique would be useful in the development of drug formations and medical agents.

  12. Pre-concentration procedure based on chitosan combined with ionic liquid for the determination of cobalt, nickel, and copper in water samples.

    PubMed

    Zawisza, Beata; Sitko, Rafal

    2013-05-01

    An environmentally friendly analytical procedure of pre-concentration of cobalt, nickel, and copper according to the rules of green chemistry has been developed. The proposed method is based on using chitosan for sorption of trace elements from water samples. The novel modification of the sorption process is the combination of an ionic liquid (1-butyl-3-methylimidazolium hexafluorophosphate [BMIM][PF6]) with chitosan. Ionic liquid partly decreases the crystallinity of the chitosan. The crystalline regions of the polymer are not accessible to metal ions. Although the ionic liquid cannot completely disrupt the crystalline domains of chitosan, it may gain in the reactive groups of the chitosan, even at the center of the particle. Consequently, the sorption of metal ions by chitosan is significantly improved. In this paper, adsorption characteristics of cobalt, nickel, and copper using newly developed sorption are studied. The effect of pH and time of chitosan activation, as well as sorption, salt concentration, some metals ion concentrations, and the amount of adsorbent on the extent of adsorption, are investigated. Chitosan with adsorbed metal ions was dissolved in acetic acid. After evaporation a solvent film formed and was then analyzed using X-ray fluorescence spectrometry (XRF). As it meets the criterion of thin samples for XRF analysis, the matrix effects can be neglected. With the proposed procedure we obtained detection limits of 7 ng mL(-1) for cobalt, 5 ng mL(-1) for nickel, and 4 ng mL(-1) for copper. PMID:23643042

  13. Comparative ecotoxicology study of two neoteric solvents: Imidazolium ionic liquid vs. glycerol derivative.

    PubMed

    Perales, Eduardo; García, Cristina Belén; Lomba, Laura; Aldea, Luis; García, José Ignacio; Giner, Beatriz

    2016-10-01

    In this study we have compared the acute ecotoxicity of two solvents, with very different structure and origin, but sharing many physical-chemical properties, so they can be used for similar purposes; a well-known ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]) and a solvent partially derived from biomass, 3-bis(2,2,2-trifluoroethoxy)propan-2-ol (BTFIP). We have used three biomodels (Vibrio fischeri, Daphnia magna and Danio rerio) and performed the comparison applying the Environmental, Health and Safety (EHS) hazard assessment. According to the results, ecotoxicity of [BMIM][PF6] and BTFIP is quite similar in the simplest model Vibrio fischeri, while in Daphnia magna [BMIM][PF6] is clearly more toxic. However, in Danio rerio, toxicity of these chemicals is again quite similar and both can be classified as "nontoxic". The higher index value of [BMIM][PF6] in water mediate effect in the EHS assessment indicates that this ionic liquid is more dangerous than BTFIP, although accumulation and degradation properties have not been taken into account. Further studies will be necessary to ascertain these conclusions. PMID:27265564

  14. Novel multifunctional nanofibers based on thermoplastic polyurethane and ionic liquid: towards antibacterial, anti-electrostatic and hydrophilic nonwovens by electrospinning.

    PubMed

    Xing, Chenyang; Guan, Jipeng; Chen, Zhouli; Zhu, Yu; Zhang, Bowu; Li, Yongjin; Li, Jingye

    2015-03-13

    Novel antibacterial, anti-electrostatic, and hydrophilic nanofibers based on a blend containing thermoplastic polyurethane (TPU) and a room-temperature ionic liquid (IL), 1-butyl-3-methylimidazolium hexafluorophosphate [BMIM][PF6], were fabricated by electrospinning. We investigated the effect of the IL on the morphology and the physical properties of the TPU nanofibers. Nanofibers with a 'bead-on-string' morphology were obtained by electrospinning from a neat TPU solution. The incorporation of the IL, at levels as low as 1 wt%, largely suppressed the formation of beads during electrospinning, and homogeneous nanofibers were obtained. The as-spun TPU/IL composite nanofibers showed significant activity against both Escherichia coli (E coli) and Staphylococcus aureus (S. aureus), with antibacterial activities of more than four and three, respectively. This means that the antibacterial efficiencies of TPU/IL composite nanofibers toward E coli and S. aureus are 99.99% and 99.9%, respectively. Moreover, nonwoven fabrics derived from the electrospun TPU/IL composite nanofibers exhibit better stretchability, elasticity, and higher electrical conductivity compared to those made using neat TPU without an IL. Additionally, the incorporation of the IL leads to a hydrophilic surface for the TPU/IL composite nanofibers compared to hydrophobic neat TPU nanofibers. These multifunctional nanofibers with excellent antibacterial, anti-electrostatic, and mechanical properties and improved hydrophilicity are promising candidates for biomedical and wastewater treatment applications.

  15. Atomic Resolution Insights into the Structural Aggregations and Optical Properties of Neat Imidazolium-Based Ionic Liquids.

    PubMed

    Du, Likai; Geng, Cuihuan; Zhang, Dongju; Lan, Zhenggang; Liu, Chengbu

    2016-07-14

    A fundamental understanding of the structural heterogeneity and optical properties of ionic liquids is crucial for their potential applications in catalysis, optical measurement, and solar cells. Herein, a synergistic approach combining molecular dynamics simulations, excited-state calculations, and statistical analysis was used to explore the explicit correlation between the structural and optical properties of one imidazolium amino acid-based ionic liquid, 1-butyl-3-methylimidazolium glycine. The estimated absorption spectrum successfully rationalizes the unusual and non-negligible absorption band beyond 300 nm for the neat imidazolium-based ionic liquid. The absorption behavior of imidazolium-based ionic liquids is shown to be sensitive to the details of their locally heterogeneous environments. We quantitatively highlight the imidazolium moiety and its various molecular aggregations, rather than the monomeric imidazolium moiety, that are responsible for the absorption characteristics. These results would improve our understanding of the preliminary interplay between structural heterogeneity and optical properties for neat imidazolium-based ionic liquids. PMID:27276660

  16. Temperature-controlled ionic liquid-based ultrasound-assisted microextraction for preconcentration of trace quantity of cadmium and nickel by using organic ligand in artificial saliva extract of smokeless tobacco products.

    PubMed

    Arain, Sadaf Sadia; Kazi, Tasneem Gul; Arain, Asma Jabeen; Afridi, Hassan Imran; Baig, Jameel Ahmed; Brahman, Kapil Dev; Naeemullah; Arain, Salma Aslam

    2015-03-01

    A new approach was developed for the preconcentration of cadmium (Cd) and nickel (Ni) in artificial saliva extract of dry snuff (brown and black) products using temperature-controlled ionic liquid-based ultrasound-assisted dispersive liquid-liquid microextraction (TIL-UDLLμE) followed by electrothermal atomic absorption spectrometry (ETAAS). The Cd and Ni were complexed with ammonium pyrrolidinedithiocarbamate (APDC), extracted in ionic liquid drops, 1-butyl-3-methylimidazolium hexafluorophosphate [C4MIM][PF6]. The multivariate strategy was applied to estimate the optimum values of experimental variables influence the % recovery of analytes by TIL-UDLLμE method. At optimum experimental conditions, the limit of detection (3s) were 0.05 and 0.14μgL(-1) while relative standard deviations (% RSD) were 3.97 and 3.55 for Cd and Ni respectively. After extraction, the enhancement factors (EF) were 87 and 79 for Cd and Ni, respectively. The RSD for six replicates of 10μgL(-1) Cd and Ni were 3.97% and 3.55% respectively. To validate the proposed method, certified reference material (CRM) of Virginia tobacco leaves was analyzed, and the determined values of Cd and Ni were in good agreement with the certified values. The concentration of Cd and Ni in artificial saliva extracts corresponds to 39-52% and 21-32%, respectively, of the total contents of both elements in dry brown and black snuff products. PMID:25523044

  17. Ultra-trace determination of lead in water and food samples by using ionic liquid-based single drop microextraction-electrothermal atomic absorption spectrometry.

    PubMed

    Manzoori, Jamshid L; Amjadi, Mohammad; Abulhassani, Jafar

    2009-06-30

    An improved single drop microextraction procedure was developed for the preconcentration of lead prior to its determination by electrothermal atomic absorption spectrometry. Ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate [C4MIM][PF6], was used as an alternative to volatile organic solvents for extraction. Lead was complexed with ammonium pyrroldinedithiocarbamate (APDC) and extracted into a 7-microL ionic liquid drop. The extracted complex was directly injected into the graphite furnace. Several variables affecting microextraction efficiency and ETAAS signal, such as pyrolysis and atomization temperature, pH, APDC concentration, extraction time, drop volume and stirring rate were investigated and optimized. In the optimum experimental conditions, the limit of detection (3s) and the enhancement factor were 0.015 microg L(-1) and 76, respectively. The relative standard deviation (RSD) for five replicate determinations of 0.2 microg L(-1) Pb was 5.2%. The developed method was validated by the analysis of certified reference materials and applied successfully to the determination of lead in several real samples. PMID:19463561

  18. Ionic liquid-based single drop microextraction combined with electrothermal atomic absorption spectrometry for the determination of manganese in water samples.

    PubMed

    Manzoori, Jamshid L; Amjadi, Mohammad; Abulhassani, Jafar

    2009-02-15

    Room temperature ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate [C(4)MIM][PF(6)], was used as an alternative to volatile organic solvents in single drop microextraction-electrothermal atomic absorption spectrometry (SDME-ETAAS). Manganese was extracted from aqueous solution into a drop of the ionic liquid after complextaion with 1-(2-thiazolylazo)-2-naphthol (TAN) and the drop was directly injected into the graphite furnace. Several variables affecting microextraction efficiency and ETAAS signal, such as pyrolysis and atomization temperature, pH, TAN concentration, extraction time, drop volume and stirring rate were investigated and optimized. In the optimum experimental conditions, the limit of detection (3s) and the enhancement factor were 0.024 microg L(-1) and 30.3, respectively. The relative standard deviation (RSD) for five replicate determinations of 0.5 microg L(-1) Mn(II) was 5.5%. The developed method was validated by the analysis of a certified reference material (NIST SRM 1643e) and applied successfully to the determination of manganese in several natural water samples. PMID:19084676

  19. High/low temperature operation of electric double layer capacitor utilizing acidic cellulose-chitin hybrid gel electrolyte

    NASA Astrophysics Data System (ADS)

    Yamazaki, Shigeaki; Takegawa, Akihiko; Kaneko, Yoshiro; Kadokawa, Jun-ichi; Yamagata, Masaki; Ishikawa, Masashi

    An acidic cellulose-chitin hybrid gel electrolyte consisting of cellulose, chitin, 1-butyl-3-methylimidazolium, 1-allyl-3-methylimidazolium bromide, and an aqueous H 2SO 4 solution is investigated for electric double layer capacitors (EDLCs) with activated carbon fiber cloth electrodes. The acidic cellulose-chitin hybrid gel electrolyte shows a high ionic conductivity comparable to that for an aqueous 2 mol dm -3 H 2SO 4 solution at 0-80 °C. This system's temperature dependence in EDLC performance is investigated by galvanostatic charge-discharge measurement. An EDLC cell with the acidic hybrid gel electrolyte has higher capacitance than that with the aqueous H 2SO 4 solution in the range of operation temperatures (-10 to 60 °C). Moreover, the capacitance retention of the EDLC cell with the acidic hybrid gel electrolyte is better than that of a cell with the H 2SO 4 solution at 60 °C over 10,000 cycles. This suggests that the proposed acidic gel electrolyte has excellent stability in the presence of a strong acid, even at a high temperature of 60 °C.

  20. Synthesis, COSMO-RS analysis and optical properties of surface modified ZnS quantum dots using ionic liquids

    NASA Astrophysics Data System (ADS)

    Shahid, Robina; Muhammad, Nawshad; Gonfa, Girma; Toprak, Muhammet S.; Muhammed, Mamoun

    2015-10-01

    Zinc sulfide (ZnS) quantum dots (QDs) were synthesized using the microwave assisted ionic liquid (MAIL) route. Three ionic liquids (ILs), namely, 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM]BF4]), trihexyl(tetradecyl) phosphonium bis(trifluoromethanesulfonyl) amide ([P6,6,6,14][TSFA]) and trihexyl(tetradecyl) phosphonium chloride ([P6,6,6,14][Cl]) were used in this study. The size and structure of the QDs were characterized by high-resolution transmission electron microscopy (HR-TEM) and selected area electron diffraction (SAED) pattern, respectively. The synthesized QDs were of wurtzite crystalline structure with size less than 5 nm. The QDs were more uniformly distributed while using the phosponium based ILs as a reaction medium during synthesis. The optical properties were investigated by UV-vis absorption and photoluminescence (PL) emission spectroscopy. The optical properties of QDs showed the quantum confinement effect in their absorption and the effect of cation and anion structural moiety was observed on their bandedge emission. The QDs emission intensity was measured higher for [P6,6,6,14][Cl] due to their better dispersion as well as high charge density of Cl anion. The capability of the ILs in stabilizing the QDs was interpreted by density functional theory (DFT) computations. The obtained results are in good agreement with the theoretical prediction.

  1. Peculiarity of the liquid/vapour interface of an ionic liquid: study of surface tension and viscoelasticity of liquid BMImPF6 at various temperatures

    NASA Astrophysics Data System (ADS)

    Halka, V.; Tsekov, R.; Freyland, W.

    2005-03-01

    We have measured the surface tension and the capillary wave spectra at the liquid/vapour interface of the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate at various temperatures up to 400 K. From the weak temperature dependence of the surface tension a low value of the surface excess entropy of 3.5 × 10-5 J K-1 m-2 results which is consistent with a strongly aligned surface layer of imidazolium cations previously predicted by MD-calculations. The capillary wave spectra recorded at different wave numbers in the range 170 cm-1q 500 cm-1 exhibit strong deviations from the behaviour expected for the free surface of simple liquids. With an extended dispersion relation including the contributions of surface dipole moment density and shear surface excess viscosity - the spectra have been analyzed. It is found that - is negligibly small, whereas substantially influences the capillary wave spectra. The electrostatic potential across the interface, which corresponds to the measured dipole moment densities, qualitatively agrees with simulation calculations. The distinct temperature dependence of suggests that with increasing temperature an order-disorder transformation occurs in the surface layer.

  2. Nanoparticles decorated with a Schiff's base for the microextraction of Cd, Pb, Ni, and Co in environmental samples.

    PubMed

    Shah, Faheem; Naeemullah; Shah, Muhammad Raza; Kazi, Tasneem Gul; Afridi, Hassan Imran; Shah, Kiramat

    2016-05-01

    In this paper, we report a new liquid-liquid microextraction procedure called "nanoparticles decorated with a Schiff's base for the microextraction of Cd, Pb, Ni, and Co in environmental samples". The developed procedure was utilized for the extraction of Cd, Pb, Ni, and Co in environmental samples. The Schiff's base was formed by reacting salicylaldehyde with 3-aminopropyltriethoxysilane-functionalized iron oxide nanoparticles. Analyte extraction was conducted in a capillary column system loaded with modified nanoparticles and triton X-114 as dispersion medium. 1-Butyl-3-methylimidazolium hexafluorophosphate was employed as an extraction solvent. Acidified methanol in ultrasonic bath was used as desorption solvent, and elemental determination was carried out with flame atomic absorption spectrometer. Characterization of modified nanoparticles was performed with FTIR spectroscopy and transmission electron microscopy. Solution pH, nanoparticles amount, dispersant concentration, ionic liquid, and temperature were optimized for the extraction. Detection limits obtained for Cd, Pb, Ni, and Co were 0.183, 0.201, 0.241, and 0.192 μg L(-1), respectively, and enhancement factors were 79.1, 86.4, 95.7, and 82.0, respectively. The reproducibility of the developed procedure was in the range of 3.98-5.10%. Validation was checked by applying the developed procedure on certified reference water samples. The microextraction based on nanoparticles decorated with Schiff's base was successfully applied for the extraction of Cd, Pb, Ni, and Co in real environmental water samples. PMID:27187842

  3. Multivariate optimization of "In capillary-Schiff's base functionalized magnetic nanoparticle based microextraction" of Pb(+2): A novel synergistic approach.

    PubMed

    Shah, Faheem; Muhammad, Haji; Naeemullah; Ullah, Azeem

    2016-07-01

    A novel microextraction procedure based on Schiff's base functionalized magnetic nanoparticles (SBMNPs) has been developed for Pb(+2) extraction. Compared to conventional microextraction systems, the main advantage of proposed procedure is that no volatile/flammable reagents have used and experimental time is also reduced. Schiff's base has been derived from salicylaldehyde and 3-aminopropyltriethoxysilane modified nanoparticles. Extraction of Pb(+2) was carried out in a capillary column containing analyte followed by the addition of SBMNPs and triton X-114 where ionic-liquid "1-Butyl-3-methylimidazolium hexafluorophosphate" was used as an extractant. After extraction; analyte concentration was determined with flame atomic absorption spectrometer through a self made micro-injection system. The SBMNPs were characterized by FTIR and TEM, respectively, demonstrating their distinct core-shell structures. Different experimental parameters were optimized through multivariate strategy. Detection limit, enhancement factor and relative standard deviation obtained with developed procedure were 0.193μgL(-1), 26.3 and 4.01%, respectively. Validity was checked through the recovery experiments and satisfactory results were obtained. In brief the synergistic combination of SBMNPs in column with ionic-liquid resulted in an efficient microextraction procedure for Pb(+2) in real samples. PMID:27154669

  4. Morphology- and facet-controlled synthesis of CuO micro/nanomaterials and analysis of their lithium ion storage properties

    NASA Astrophysics Data System (ADS)

    Liu, Xiaodi; Liu, Guangyin; Wang, Lijuan; Li, Yinping; Ma, Yupei; Ma, Jianmin

    2016-04-01

    Hierarchical CuO architectures and monodisperse CuO nanoplates are synthesized via a hydrothermal method with the assistance of ionic liquid 1-butyl-3-methylimidazolium chloride ([Bmim]Cl). The products are characterized by XRD, SEM, TEM, HRTEM, BET, and XPS, and the results indicate that the CuO architectures are composed of nanosheets with exposed (001) facets and the CuO nanoplates are single crystals enclosed by (200) facets. More specially, it is found that [Bmim]Cl serves as an effective template for the synthesis of CuO nanoplates by adsorbing on the (200) planes of monoclinic CuO. When evaluated as anode materials for lithium-ion batteries, CuO architectures possess higher discharge capacity, better cycling stability, and better rate capability than CuO nanoplates. The initial discharge capacity of CuO architectures is 1096 mAh g-1 at a rate of 0.5 C, whereas CuO nanoplates exhibit a lower capacity of 878.4 mAh g-1. Moreover, after 50 cycles, CuO architectures and CuO nanoplates can deliver discharge capacities of 465.6 and 281.6 mAh g-1, respectively.

  5. Pt-Pd bimetallic nanoparticles dispersed in an ionic liquid and peroxidase immobilized on nanoclay applied in the development of a biosensor.

    PubMed

    Pusch, Jessica M E; Brondani, Daniela; Luza, Leandro; Dupont, Jairton; Vieira, Iolanda C

    2013-09-01

    Pt-Pd bimetallic alloy nanoparticles (NPs) dispersed in the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (Pt-Pd-BMI·PF6) were employed together with a peroxidase (PO) enzyme from cauliflower immobilized on nanoclay for the development of a new biosensor for polyphenol determination by square-wave voltammetry (SWV). The biosensor demonstrated good repeatability and reproducibility, low limit of detection (LOD = 3.7 × 10(-7) mol L(-1) for caffeic acid (CA)), and adequate lifetime and stability (maintaining over 80% of the response over 80 days of evaluation, and allowing over 600 measurements by SWV for each electrode). Under optimized conditions, the proposed biosensor was applied in the determination of the bioelectrochemical polyphenolic index (BPI) for samples of commercial white wine, using CA as the phenolic compound standard. The recovery of CA from wine samples ranged from 95.5 to 108.3%. The values for the polyphenolic content obtained using the proposed biosensor showed a good correlation (r = 0.990) with those obtained with the reference spectrophotometric method (Folin-Ciocalteu method). Therefore, the proposed biosensor represents a useful tool for the rapid and accurate monitoring of polyphenolic content in wine samples and may also be applicable to other beverage samples, such as juices and teas.

  6. Matrix solid-phase dispersion coupled with magnetic ionic liquid dispersive liquid-liquid microextraction for the determination of triazine herbicides in oilseeds.

    PubMed

    Wang, Yuanpeng; Sun, Ying; Xu, Bo; Li, Xinpei; Wang, Xinghua; Zhang, Hanqi; Song, Daqian

    2015-08-12

    A novel method was developed for the determination of six triazine herbicides from oilseeds by matrix solid-phase dispersion combined with magnetic ionic liquid dispersive liquid-liquid microextraction (MSPD-MIL-DLLME), followed by ultrafast liquid chromatography with ultraviolet detection (UFLC-UV). The MIL, 1-butyl-3-methylimidazolium tetrachloroferrate ([C4mim][FeCl4]), was used as the microextraction solvent to simplify the extraction procedure by magnetic separation. The effects of several important experimental parameters, including type of dispersant, ratio of sample to dispersant, type and volume of collected elution solvent, type and volume of MIL, were investigated. Using the present method, UFLC-UV gave the limits of detection (LODs) of 1.20-2.72 ng g(-1) and the limits of quantification (LOQs) of 3.99-9.06 ng g(-1) for triazine herbicides. The recoveries were ranged from 82.9 to 113.7% and the relative standard deviations (RSDs) were equal or lower than 7.7%. The present method is easy-to-use and effective for extraction of triazine herbicides from oilseeds and shows the potentials of practical applications in the treatment of the fatty solid samples.

  7. Dielectric spectra of ionic liquids and their conversion to solvation dynamics: a detailed computational analysis of polarizable systems.

    PubMed

    Schmollngruber, Michael; Schröder, Christian; Steinhauser, Othmar

    2014-06-14

    For the three molecular ionic liquids 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate and 1-butyl-3-methylimidazolium tetrafluoroborate, dielectric spectra were calculated from molecular dynamics simulations based on polarizable force fields. Using the reaction field continuum model the dielectric spectra were converted to the solvation dynamics of coumarin 153. It is shown in detail that the inclusion of the static conductivity in this model is essential. When simplifying the dielectric spectrum to the static conductivity hyperbola, the solvation response function becomes mono-exponential. Taking into account the frequency dependence of the conductivity, the typical two time-regimes of the solvation response function in ionic liquids are already obtained. However, the mean relaxation time remains the same. When converting the complete dielectric spectrum, i.e. also including frequency-dependent dielectric permittivity, quantitative changes are observed, but the qualitative shape is conserved. In accordance with previous experimental studies, solvation dynamics in ionic liquids predicted by the reaction field continuum model is too fast for longer times. This correlates with the suppression of the fine structure of the dielectric spectrum at low frequencies by the static conductivity hyperbola. By scaling down the static conductivity this effect can be partially amended. In addition to the impact of the solvent dielectric spectrum on solvation dynamics, solute-specific effects, i.e. anisotropy in shape and charge distribution as well as polarizability, were also studied.

  8. Ionic liquid-induced formation of the α-helical structure of β-lactoglobulin.

    PubMed

    Takekiyo, Takahiro; Koyama, Yoshihiro; Yamazaki, Kumiko; Abe, Hiroshi; Yoshimura, Yukihiro

    2013-09-01

    Structural modification of bovine milk β-lactoglobulin (β-LG) in aqueous 1-butyl-3-methylimidazolium nitrate ([bmim][NO3]) and ethylammonium nitrate ([EAN][NO3]) solutions has been investigated by Fourier transform infrared and circular dichroism spectroscopy. Remarkably, high ionic liquid (IL) concentrations (>15 mol %IL) caused formation of a non-native α-helical structure of β-LG and disruption of its tertiary structure. Furthermore, while [bmim][NO3] promoted protein aggregation, [EAN][NO3] inhibited it probably owing to differences in the unique solution structure (nanoheterogeneity) of the ILs by the different cationic species. The IL-induced α-helical formation of β-LG shows a behavior similar to the alcohol denaturation, but a disordered structure-rich state was observed in the β-α transition process by adding IL, in contrast to the case of an aqueous alcohol solution of protein. We propose that the molten salt-like property of aqueous IL solutions strongly support α-helical formation of proteins.

  9. Understanding positive and negative deviations in polarity of ionic liquid mixtures by pseudo-solvent approach.

    PubMed

    Beniwal, Vijay; Kumar, Anil

    2016-08-24

    Physico-chemical properties of liquid mixtures in general display large deviations from linear behaviour, arising out of complex specific and non-specific intermolecular interactions. The polarity of liquid mixtures displaying large positive and negative deviations can be minimized and linear mixing can be achieved in liquids using a pseudo-solvent methodology. The work described herein is designed to investigate the influence of different physical parameters on the linear pseudo-solvent composition in ionic liquid mixtures. For this purpose, we have determined the deviations from linearity, ΔE values (defined as given by ) for binary mixtures of a variety of ionic liquids, including two molecular solvents, DMSO and formamide. Firstly, the investigations were carried out in three 1-butyl-3-methylimidazolium cation based aprotic ionic liquids and the roles of anionic structure and hydrogen bond acceptor basicities (β values) of the ionic liquids were determined. The influence of the cationic structure, i.e., the hydrogen bond donor acidity (α values) and non-associative nature of the ionic liquids, was determined using C2-methylated analogs, 1-butyl-2,3-dimethylimidazolium cation based ionic liquids. The role of the protic nature of ionic liquids was studied in two protic ionic liquids, viz., 1-methylimidazolium formate and 1-methylimidazolium acetate. The effects of the temperature, pseudo-solvent structure and solvatochromic probe structure on the ΔE values were also explored. PMID:27523572

  10. Esterification of potato starch by a biocatalysed reaction in an ionic liquid.

    PubMed

    Zarski, Arkadiusz; Ptak, Sylwia; Siemion, Przemyslaw; Kapusniak, Janusz

    2016-02-10

    In this study, potato starch was esterified with oleic acid, using 1-butyl-3-methylimidazolium chloride as a reaction medium and an immobilised lipase from Thermomyces lanuginosus as a catalyst. The degree of substitution (DS) of the products was determined by the volumetric method; and the best esterified product (with the highest DS) was determined by an elemental analysis. The effect of the reaction parameters on the DS, such as the time and the temperature, were also studied. The product with the highest DS (0.22) was found in the reaction carried out at 60 °C for 4h. Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) analyses confirmed the esterification of the potato starch. Furthermore, the results of X-ray diffraction (XRD) and a scanning electron microscopy (SEM) revealed that the crystallinity and the morphology of the native potato starch was slightly changed during its partial gelatinisation in the ionic liquid, and was completely destroyed as a result of the formation of the esters. The thermal stability of the starch oleate decreased, when compared to the unmodified starch, as was indicated by a thermal gravimetric analysis (TGA).

  11. Effect of water on structure and dynamics of [BMIM][PF6] ionic liquid: An all-atom molecular dynamics simulation investigation

    NASA Astrophysics Data System (ADS)

    Sharma, Anirban; Ghorai, Pradip Kr.

    2016-03-01

    Composition dependent structural and dynamical properties of aqueous hydrophobic 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]) ionic liquid (IL) have been investigated by using all-atom molecular dynamics simulation. We observe that addition of water does not increase significant number of dissociated ions in the solution over the pure state. As a consequence, self-diffusion coefficient of the cation and anion is comparable to each other at all water concentration similar to that is observed for the pure state. Voronoi polyhedra analysis exhibits strong dependence on the local environment of IL concentration. Void and neck distributions in Voronoi tessellation are approximately Gaussian for pure IL but upon subsequent addition of water, we observe deviation from the Gaussian behaviour with an asymmetric broadening with long tail of exponential decay at large void radius, particularly at higher water concentrations. The increase in void space and neck size at higher water concentration facilitates ionic motion, thus, decreasing dynamical heterogeneity and IL reorientation time and increases self-diffusion coefficient significantly.

  12. Unusual solvatochromic absorbance probe behaviour within mixtures of poly(ethylene glycol)-400 + ionic liquid, [bmim][Tf2N

    NASA Astrophysics Data System (ADS)

    Ali, Anwar; Ali, Maroof; Malik, Nisar Ahmad; Uzair, Sahar

    2014-03-01

    The potentially green solvents made up of ionic liquids (ILs) and poly(ethylene glycols) may have wide range of the applications in many chemical and biochemical fields. In the present work, solvatochromic absorbance probe behaviour is used to assess the physicochemical properties of the mixtures composed of PEG-400 + IL, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [bmim][Tf2N]. Lowest energy intramolecular charge-transfer absorbance maxima of a betaine dye, i.e., ETN , indicates the dipolarity/polarizability and/or hydrogen-bond donating (HBD) acidity of the [bmim][Tf2N] + PEG-400 mixtures to be even higher than that of neat [bmim][Tf2N], the solution component with higher dipolarity/polarizability and/or HBD acidity. Dipolarity/polarizability (π∗) obtained separately from the electronic absorbance response of probe N,N-diethyl-4-nitroaniline, and the HBD acidity (α) of PEG-400 + [bmim][Tf2N] mixtures are also observed to be anomalously high. A comparative study of the PEG + IL mixtures has also been done with PEG-400 + molecular organic solvents (protic polar [methanol], aprotic polar [N,N-dimethylformamide], and non polar, [benzene]) mixtures, but these mixtures do not show this type of unusual behaviour. A four-parameter simplified combined nearly ideal binary solvent/Redlich-Kister (CNIBS/R-K) equation is shown to satisfactorily predict the solvatochromic parameters within PEG-400 + different solvent mixtures.

  13. Syntheses and crystal structures of benzene-sulfonate and -carboxylate copper polymers and their application in the oxidation of cyclohexane in ionic liquid under mild conditions.

    PubMed

    Hazra, Susanta; Ribeiro, Ana P C; Guedes da Silva, M Fátima C; Nieto de Castro, Carlos A; Pombeiro, Armando J L

    2016-09-21

    The syntheses, crystal structures and catalytic activities of the polymers derived from 2-(2-pyridylmethyleneamino)benzenesulfonic acid (HL), viz. [CuL(H2tma)]n (1) and [{Cu2L2(H2pma)}·(8H2O)]n (2) [H3tma = benzene-1,3,5-tricarboxylic (trimesic) acid and H4pma = benzene-1,2,4,5-tetracarboxylic (pyromellitic) acid], are presented. Despite the comparable combinations and compositions of ligands (sulfonate and carboxylate) in these two polymers the bridging moiety in 1 is sulfonate while in 2 it is carboxylate. Complexes 1 and 2 act as catalysts in the peroxidative oxidation of cyclohexane under mild conditions using either the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate [bmim][PF6] or acetonitrile as the solvent. The ionic liquid medium leads to increases in the yields and in the turnover numbers, achieved in shorter reaction times in comparison with those when using the conventional acetonitrile solvent. A simple recycling of the catalysts in the ionic liquid medium is achieved without loss of activity and selectivity.

  14. Ionic liquid-assisted sonochemical preparation of CeO2 nanoparticles for CO oxidation

    DOE PAGES

    Alammar, Tarek; Noei, Heshmat; Wang, Yuemin; Grünert, Wolfgang; Mudring, Anja -Verena

    2014-10-10

    CeO2 nanoparticles were synthesized via a one-step ultrasound synthesis in different kinds of ionic liquids based on bis(trifluoromethanesulfonylamide, [Tf2N]–, in combination with various cations including 1-butyl-3-methylimidazolium ([C4mim]+), 1-ethyl-2,3-dimethylimidazolium ([Edimim]+), butyl-pyridinium([Py4]+), 1-butyl-1-methyl-pyrrolidinium ([Pyrr14]+), and 2-hydroxyethyl-trimethylammonium ([N1112OH]+). Depending on synthetic parameters, such as ionic liquid, Ce(IV) precursor, heating method, and precipitator, formed ceria exhibits different morphologies, varying from nanospheres, nanorods, nanoribbons, and nanoflowers. The morphology, crystallinity, and chemical composition of the obtained materials were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDX), Raman spectroscopy, and N2 adsorption. The structural and electronic propertiesmore » of the as-prepared CeO2 samples were probed by CO adsorption using IR spectroscopy under ultrahigh vacuum conditions. The catalytic activities of CeO2 nanoparticles were investigated in the oxidation of CO. CeO2 nanospheres obtained sonochemically in [C4mim][Tf2N] exhibit the best performance for low-temperature CO oxidation. As a result, the superior catalytic performance of this material can be related to its mesoporous structure, small particle size, large surface area, and high number of surface oxygen vacancy sites.« less

  15. A novel architecture based upon multi-walled carbon nanotubes and ionic liquid to improve the electroanalytical detection of ciprofibrate.

    PubMed

    Vicentini, Fernando Campanhã; Elisa Ravanini, Amanda; Silva, Tiago Almeida; Janegitz, Bruno C; Zucolotto, Valtencir; Fatibello-Filho, Orlando

    2014-08-21

    Voltammetric studies have been carried out using a glassy carbon electrode (GCE) modified with multi-walled carbon nanotubes (MWCNTs) and the ionic liquid 1-butyl-3-methylimidazolium chloride (IL). Studies on the electrochemical properties of GCEs modified with MWCNTs and IL within different polymeric films (dihexadecylphosphate (DHP), Nafion, and chitosan (CTS)) were performed using a [Fe(CN)6](4-/3-) electrochemical probe. The modified GCE with different polymeric films was also tested for ciprofibrate (CPF) sensing in the presence and absence of IL in the film. The presence of IL and the MWCNTs improved the electrochemical response for CPF in all cases due to a synergic effect, and the IL-MWCNTs-DHP/GCE showed a great voltammetric profile for CPF detection. The IL-MWCNTs-DHP/GCE and differential pulse voltammetry (DPV) were used for the determination of CPF. An analytical curve was obtained for CPF in the concentration range of 2.50 × 10(-7) to 7.41 × 10(-6) mol L(-1) with a detection limit of 9.20 × 10(-8) mol L(-1). The proposed DPV method was successfully applied for CPF determination in pharmaceutical samples, and the results obtained agree with the results obtained using a spectrophotometric method at a confidence level of 95%.

  16. Room-temperature ionic liquids as electrolytes in electroanalytical determination of traces of 2-furaldehyde from oil and related wastewaters from refining processes.

    PubMed

    Shamsipur, Mojtaba; Beigi, Ali Akbar Miran; Teymouri, Mohammad; Ghorbani, Yousefali; Irandoust, Mohsen; Mehdizadeh, Ali

    2010-04-15

    Three different ionic liquids, 1-ethyl-3-methylimidazolium tetrafluoroborate, [EMIM][BF(4)]; 1-butyl-3-methylimidazolium trifluoromethanesulfonate, [BMIM][OTf]; and 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide [bmpyrr][NTf(2)] were studied as electrolytes in the electroanalytical quantification of 2-furaldehyde using square wave and differential pulse voltammetries. On applying a cathodic scan, a well-defined 2-electron wave was observed corresponding to the reduction of 2-furaldehyde to furfuryl alcohol. The electrochemical stability of the ionic liquids as electrolytes for analytical aspects and electrokinetic studies was investigated using a glassy carbon electrode (GCE). The measurements were carried out in a designed double-wall three-electrode cell, using two platinum wires as the quasi-reference and counter electrodes. Differential pulse voltammetry was found to be the most sensitive method at GCE. The detection limits of 1.4, 19.0 and 2.5 microg g(-1) were obtained for the determination of 2-furaldehyde in [EMIM][BF(4)], [BMIM][OTf] and [BMPyrr][NTf(2)], respectively. At a concentration of 50 microg g(-1), the maximum relative standard deviation (n=3) was 4.9%. The effect of water content of the ionic liquids on their potential windows and waveforms was also investigated. The proposed method was successfully applied to the determination of 2-furaldehyde in real samples, especially in oil matrices.

  17. New Alkylether-Thiazolium Room-Temperature Ionic Liquid Lubricants: Surface Interactions and Tribological Performance.

    PubMed

    Espinosa, Tulia; Sanes, José; Bermúdez, María-Dolores

    2016-07-20

    The use of newly synthesized alkylether-thiazolium ionic liquids as lubricants is described for the first time. Two ionic liquids composed of a thiazolium cation and a bis(trifluoromethanesulfonyl)amide ([Th][Tf2N]) or dicyanamide ([Th][(NC)2N]) anion have been studied, and their tribological behavior has been compared with that of 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide ([Im][Tf2N]) in pin-on-disk tests using sapphire balls against AISI 52100 or AISI 316L steels. All ionic liquids show higher contact angles on AISI 316L steel than on AISI 52100, the lowest values found for ([Im][Tf2N]) on both steel surfaces. AISI 52100 shows similar friction coefficients for all lubricants, and negligible wear rates for the ionic liquids containing the bis(trifluoromethanesulfonyl)amide anion. Immersion tests show no corrosion of AISI 52100 in imidazolium or thiazolium bis(trifluoromethanesulfonyl)amide ionic liquids. AISI 316L shows similar friction coefficients for both bis(trifluoromethanesulfonyl)amide ionic liquids, but the lowest wear rate is obtained for [Th][Tf2N]. An increase in friction coefficient and wear rate is observed for thiazolium dicyanamide. This increase is related to a tribocorrosion process due to decomposition of the thiazolium cation. XPS shows the formation of iron sulfide on the wear track on AISI 316L after lubrication with thiazolium dicyanamide. No tribocorrosion processes take place for the [Tf2N] ionic liquids. PMID:27348604

  18. Ionic liquid-assisted solvothermal synthesis of hollow Mn2O3 anode and LiMn2O4 cathode materials for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    He, Xin; Wang, Jun; Jia, Haiping; Kloepsch, Richard; Liu, Haidong; Beltrop, Kolja; Li, Jie

    2015-10-01

    Mn-based Mn2O3 anode and LiMn2O4 cathode materials are prepared by a solvothermal method combined with post annealing process. Environmentally friendly ionic liquid 1-Butyl-3-methylimidazolium tetrafluoroborate as both structure-directing agent and fluorine source is used to prepare hollow polyhedron MnF2 precursor. Both target materials Mn2O3 anode and LiMn2O4 cathode have the morphology of the MnF2 precursor. The Mn2O3 anode using carboxymethyl cellulose as binder could deliver slight better electrochemical performance than the one using poly (vinyldifluoride) as binder. The former has an initial charge capacity of 800 mAh g-1 at a current density of 101.8 mA g-1, and exhibits no obvious capacity decay for 150 cycles at 101.8 mA g-1. The LiMn2O4 cathode material prepared with molten salt assistant could display much better electrochemical performance than the one prepared without molten salt assistance. In particular, it has an initial discharge capacity of 117.5 mAh g-1 at a current density of 0.5C and good rate capability. In the field of lithium ion batteries, both the Mn2O3 anode and LiMn2O4 cathode materials could exhibit enhanced electrochemical performance due to the well formed morphology based on the ionic liquid-assisted solvothermal method.

  19. Highly Luminescent Salts Containing Well-Shielded Lanthanide-Centered Complex Anions and Bulky Imidazolium Countercations

    SciTech Connect

    Tang, Si-Fu; Lorbeer, Chantal; Wang, Xinjiao; Ghosh, Pushpal; Mudring, Anja-Verena

    2014-09-02

    Four salts containing imidazolium cations and europium(III)- or terbium(III)-centered complex anions have been successfully synthesized from an ethanol/H2O solution. The single-crystal X-ray diffraction analyses reveal that these compounds have a common formula of [R][Ln(DETCAP)4] [R = 1-ethyl-3-methylimidazolium (C2mim), Ln = Eu (1) and Tb (2); R = 1-butyl-3-methylimidazolium (C4mim), Ln = Eu (3) and Tb (4); DETCAP = diethyl-2,2,2-trichloroacetylphosphoramidate], in which the lanthanide centers are chelated by four chelating pseudo-β-diketonate ligands (DETCAP)-, forming the respective complex anions. Their thermal behaviors and stabilities were also investigated to study the role of the length of the side chain in the cations. Fluorescence measurements at both room temperature and liquid-nitrogen temperature show that these materials show intense characteristic europium(III) or terbium(III) emissions and have long decay times. Their overall quantum yields were determined to be in the range of 30–49%.

  20. Solubility and solvation of monosaccharides in ionic liquids†

    PubMed Central

    Teles, Ana Rita R.; Dinis, Teresa B. V.; Capela, Emanuel V.; Santos, Luís M. N. B. F.; Pinho, Simão P.; Freire, Mara G.; Coutinho, João A. P.

    2016-01-01

    Herein, solubility experimental data for six monosaccharides, viz. d-(+)-glucose, d-(+)-mannose, d-(−)-fructose, d-(+)-galactose, d-(+)-xylose and l-(+)-arabinose, in four ionic liquids (ILs), at temperatures ranging from 288.2 to 348.2 K, were obtained aimed at gathering a better understanding of their solvation ability and molecular-level mechanisms which rule the dissolution process. To ascertain the chemical features that enhance the solubility of monosaccharides, ILs composed of dialkylimidazolium or tetraalkylphosphonium cations combined with the dicyanamide, dimethylphosphate or chloride anions were investigated. It was found that the ranking of the solubility of monosaccharides depends on the IL; yet, d-(+)-xylose is always the most soluble while d-(−)-fructose is the least soluble monosaccharide. The results obtained show that both the IL cation and the anion play a major role in the solubility of monosaccharides. Finally, from the determination of the respective thermodynamic properties of solution, it was found that enthalpic contributions are dominant in the solubilization process. However, the observed differences in the solubilities of monosaccharides in 1-butyl-3-methylimidazolium dicyanamide are ruled by a change in the entropy of solution. PMID:27380720