Shekibi, Youssof; Rüther, Thomas; Huang, Junhua; Hollenkamp, Anthony F
2012-04-07
Replacement of volatile and combustible electrolytes in conventional lithium batteries is desirable for two reasons: safety concerns and increase in specific energy. In this work we consider the use of an ionic organic plastic crystal material (IOPC), N-ethyl-N-methylpyrrolidinium tetrafluoroborate, [C2mpyr][BF(4)], as a solid-state electrolyte for lithium battery applications. The effect of inclusion of 1 to 33 mol% lithium tetrafluoroborate, LiBF(4), into [C2mpyr][BF(4)] has been investigated over a wide temperature range by differential scanning calorimetry (DSC), impedance spectroscopy, cyclic voltammetry and cycling of full Li|LiFePO(4) batteries. The increases in ionic conductivity by orders of magnitude observed at higher temperature are most likely associated with an increase in Li ion mobility in the highest plastic phase. At concentrations >5 mol% LiBF(4) the ionic conductivity of these solid-state composites is comparable to the ionic conductivity of room temperature ionic liquids. Galvanostatic cycling of Li|Li symmetrical cells showed that the reversibility of the lithium metal redox reaction at the interface of this plastic crystal electrolyte is sufficient for lithium battery applications. For the first time we demonstrate an all solid state lithium battery incorporating solid electrolytes based on IOPC as opposed to conventional flammable organic solvents.
Functioning of inorganic/organic battery separators in silver-zinc cells
NASA Technical Reports Server (NTRS)
Philipp, W. H.; May, C. E.
1976-01-01
The results of three experimental studies related to the inorganic/organic battery separator operating mechanism are described: saponification of the plasticizer, resistivity of the simulated separators, and zincate diffusion through the separators. The inorganic/organic separator appears to be a particular example of a general class of ionic conducting films composed of inorganic fillers and/or substrates bonded together by an organic polymer containing an incompatible plasticizer that may be leached by the electrolyte. The I/O separator functions as a microporous film of varying tortuosity with essentially no specific chemical inhibition to zincate diffusion.
Jin, Liyu; Nairn, Kate M; Forsyth, Craig M; Seeber, Aaron J; MacFarlane, Douglas R; Howlett, Patrick C; Forsyth, Maria; Pringle, Jennifer M
2012-06-13
Understanding the ion transport behavior of organic ionic plastic crystals (OIPCs) is crucial for their potential application as solid electrolytes in various electrochemical devices such as lithium batteries. In the present work, the ion transport mechanism is elucidated by analyzing experimental data (single-crystal XRD, multinuclear solid-state NMR, DSC, ionic conductivity, and SEM) as well as the theoretical simulations (second moment-based solid static NMR line width simulations) for the OIPC diethyl(methyl)(isobutyl)phosphonium hexafluorophosphate ([P(1,2,2,4)][PF(6)]). This material displays rich phase behavior and advantageous ionic conductivities, with three solid-solid phase transitions and a highly "plastic" and conductive final solid phase in which the conductivity reaches 10(-3) S cm(-1). The crystal structure shows unique channel-like packing of the cations, which may allow the anions to diffuse more easily than the cations at lower temperatures. The strongly phase-dependent static NMR line widths of the (1)H, (19)F, and (31)P nuclei in this material have been well simulated by different levels of molecular motions in different phases. Thus, drawing together of the analytical and computational techniques has allowed the construction of a transport mechanism for [P(1,2,2,4)][PF(6)]. It is also anticipated that utilization of these techniques will allow a more detailed understanding of the transport mechanisms of other plastic crystal electrolyte materials.
NASA Astrophysics Data System (ADS)
Karuppasamy, K.; Vani, C. Vijil; Nichelson, A.; Balakumar, S.; Shajan, X. Sahaya
2013-06-01
In the present study, the filler chitosan was converted into nanochitosan by ionotropic gelation method. Plasticized nanocomposite solid polymer electrolytes (PNCSPE) composed of poly ethylene oxide as host polymer, LiBOB (lithium bis(oxalatoborate)) as salt, SN as plasticizer and nanochitosan as filler were prepared by membrane hot-press technique. Succinonitrile and nanochitosan incorporation in PEO-LiBOB matrix enhanced the room temperature ionic conductivity. The highest ionic conductivities were found to be in the order of 10-3.2 S/cm.
Highly Efficient Plastic Crystal Ionic Conductors for Solid-state Dye-sensitized Solar Cells
Hwang, Daesub; Kim, Dong Young; Jo, Seong Mu; Armel, Vanessa; MacFarlane, Douglas R.; Kim, Dongho; Jang, Sung-Yeon
2013-01-01
We have developed highly efficient, ambient temperature, solid-state ionic conductors (SSICs) for dye-sensitized solar cells (DSSCs) by doping a molecular plastic crystal, succinonitrile (SN), with trialkyl-substituted imidazolium iodide salts. High performance SSICs with enhanced ionic conductivity (2–4 mScm−1) were obtained. High performance solid-state DSSCs with power conversion efficiency of 7.8% were fabricated using our SSICs combined with unique hierarchically nanostructured TiO2 sphere (TiO2-SP) photoelectrodes; these electrodes have significant macroporosity, which assists penetration of the solid electrolyte into the electrode. The performance of our solid-state DSSCs is, to the best of our knowledge, the highest reported thus far for cells using plastic crystal-based SSICs, and is comparable to that of the state-of-the-art DSSCs which use ionic liquid type electrolytes. This report provides a logical strategy for the development of efficient plastic crystal-based SSICs for DSSCs and other electrochemical devices. PMID:24343425
NASA Astrophysics Data System (ADS)
Das, S.; Ghosh, A.
2016-05-01
We have studied ionic conductivity and dielectric permittivity of PEO-LiClO4 solid polymer electrolyte plasticized with polyethylene glycol (PEG). The temperature dependence of the ionic conductivity has been well interpreted using Vogel-Tamman-Fulcher equation. The maximum dielectric constant is observed for 30 wt. % of PEG content. To get further insights into the ion dynamics, the complex dielectric permittivity has been studied with Havriliak-Negami function. The variation of relaxation time with inverse temperature obtained from HN formalism follows VTF nature.
[Neuronal and synaptic properties: fundamentals of network plasticity].
Le Masson, G
2000-02-01
Neurons, within the nervous system, are organized in different neural networks through synaptic connections. Two fundamental components are dynamically interacting in these functional units. The first one are the neurons themselves, and far from being simple action potential generators, they are capable of complex electrical integrative properties due to various types, number, distribution and modulation of voltage-gated ionic channels. The second elements are the synapses where a similar complexity and plasticity is found. Identifying both cellular and synaptic intrinsic properties is necessary to understand the links between neural networks behavior and physiological function, and is a useful step towards a better control of neurological diseases.
Ahmad, N H; Isa, M I N
2016-02-10
Two solid biopolymer electrolytes (SBEs) systems of carboxymethyl cellulose doped ammonium chloride (CMC-AC) and propylene carbonate plasticized (CMC-AC-PC) were prepared via solution casting technique. The ionic conductivity of SBEs were analyzed using electrical impedance spectroscopy (EIS) in the frequency range of 50 Hz-1 MHz at ambient temperature (303K). The highest ionic conductivity of CMC-AC SBE is 1.43 × 10(-3)S/cm for 16 wt.% of AC while the highest conductivity of plasticized SBE system is 1.01 × 10(-2)S/cm when added with 8 wt.% of PC. TGA/DSC showed that the addition of PC had increased the decomposition temperature compared of CMC-AC SBE. Fourier transform infrared (FTIR) spectra showed the occurrence of complexation between the SBE components and it is proved successfully executed by Gaussian software. X-ray diffraction (XRD) indicated that amorphous nature of SBEs. It is believed that the PC is one of the most promising plasticizer to enhance the ionic conductivity and performance for SBE system. Copyright © 2015 Elsevier Ltd. All rights reserved.
Role of succinonitrile in improving ionic conductivity of sodium-ion conductive polymer electrolyte
NASA Astrophysics Data System (ADS)
Nair, Manjula G.; Mohapatra, Saumya R.
2018-05-01
Sodium ion conducting solid polymer electrolytes were prepared using poly (ethylene oxide) (PEO) as polymer matrix, sodium perchlorate (NaClO4) as salt and succinonitrile (SN) as a plasticizer by solution casting technique. By blending a plastic crystal such as succinonitrile (SN) with PEO-NaClO4 electrolyte system, we aimed at improving the ionic conductivity by weakening the ether oxygen-Na+ interactions. The XRD and FTIR studies revealed structural and micro-structural changes in the blended electrolytes which aids in improving ionic conductivity. Also, DSC measurements showed improved segmental motion in the blended polymer electrolytes due to plasticizing effect of SN. The maximum ionic conductivity observed at room temperature is 1.13×10-5 S cm-1 merely for 7 wt. % of SN, which is one order higher than pure polymer-salt complex. The thermo-gravimetric analysis (TGA) suggests that blending of SN with polymer electrolyte had no detrimental effect on its thermal stability.
NASA Astrophysics Data System (ADS)
Vilbaste, M.; Heinonen, M.; Saks, O.; Leito, I.
2013-08-01
The purpose of this paper is to study the effect of contaminated water in the context of humidity generators. Investigation of different methods to determine the drop in dew-point temperature due to contamination and experiments on actual contamination rates are reported. Different methods for calculating the dew-point temperature effect from electrical conductivity and density measurements are studied with high-purity water and aqueous solutions of NaCl and LiCl. The outcomes of the calculation methods are compared with the results of direct humidity measurements. The results show that the often applied Raoult's law based calculation method is in good agreement with other methods. For studying actual contamination, water samples were kept in glass, plastic, copper and stainless-steel vessels for up to 13 months to investigate natural ionic and organic contamination in vessels with different wall materials. The amount of ionic contamination was found to be higher in copper and glass vessels than in stainless-steel and plastic vessels. The amount of organic contamination was found to be highest in the plastic vessel. In all the cases, however, the corresponding drop in dew-point temperature due to natural contamination was found to be below 0.1 mK. The largest rate of change of dew-point temperature was 26 µK/month. Thus, if proper cleanness is maintained in a humidity generator the effect of contamination of water in the saturator is insignificant compared with the major uncertainty components even in the most accurate generators today.
NASA Astrophysics Data System (ADS)
Chai, M. N.; Isa, M. I. N.
2016-06-01
The plasticized solid bio-polymer electrolytes (SBEs) system has been formed by introducing glycerol (Gly) as the plasticizer into the carboxymethyl cellulose (CMC) doped with oleic acid (OA) via solution casting techniques. The ionic conductivity of the plasticized SBEs has been studied using Electrical Impedance Spectroscopy. The highest conductivity achieved is 1.64 × 10-4 S cm-1 for system containing 40 wt. % of glycerol. FTIR deconvolution technique had shown that the conductivity of CMC-OA-Gly SBEs is primarily influenced by the number density of mobile ions. Transference number measurement has shown that the cation diffusion coefficient and ionic mobility is higher than anion which proved the plasticized polymer system is a proton conductor.
Romanenko, Konstantin; Pringle, Jennifer M; O'Dell, Luke A; Forsyth, Maria
2015-07-15
Organic ionic plastic crystals (OIPCs) show strong potential as solid-state electrolytes for lithium battery applications, demonstrating promising electrochemical performance and eliminating the need for a volatile and flammable liquid electrolyte. The ionic conductivity (σ) in these systems has recently been shown to depend strongly on polycrystalline morphology, which is largely determined by the sample's thermal history. [K. Romanenko et al., J. Am. Chem. Soc., 2014, 136, 15638]. Tailoring this morphology could lead to conductivities sufficiently high for battery applications, so a more complete understanding of how phenomena such as solid-solid phase transitions can affect the sample morphology is of significant interest. Anisotropic relaxation of nuclear spin magnetisation provides a new MRI based approach for studies of polycrystalline materials at both a macroscopic and molecular level. In this contribution, morphology alterations induced by solid-solid phase transitions in triisobutyl(methyl)phosphonium bis(fluorosulfonyl)imide (P1444FSI) and diethyl(methyl)(isobutyl)phosphonium hexafluorophosphate (P1224PF6) are examined using magnetic resonance imaging (MRI), alongside nuclear magnetic resonance (NMR) spectroscopy, diffusion measurements and conductivity data. These observations are linked to molecular dynamics and structural behaviour crucial for the conductive properties of OIPCs. A distinct correlation is established between the conductivity at a given temperature, σ(T), and the intensity of the narrow NMR signal that is attributed to a mobile fraction, fm(T), of ions in the OIPC. To explain these findings we propose an analogy with the well-studied relationship between permeability (k) and void fraction (θ) in porous media, with k(θ) commonly quantified by a power-law dependence that can also be employed to describe σ(fm).
Shlyonsky, Vadim
2013-12-01
In the present article, a novel model of artificial membranes that provides efficient assistance in teaching the origins of diffusion potentials is proposed. These membranes are made of polycarbonate filters fixed to 12-mm plastic rings and then saturated with a mixture of creosol and n-decane. The electrical resistance and potential difference across these membranes can be easily measured using a low-cost volt-ohm meter and home-made Ag/AgCl electrodes. The advantage of the model is the lack of ionic selectivity of the membrane, which can be modified by the introduction of different ionophores to the organic liquid mixture. A membrane treated with the mixture containing valinomycin generates voltages from -53 to -25 mV in the presence of a 10-fold KCl gradient (in to out) and from -79 to -53 mV in the presence of a bi-ionic KCl/NaCl gradient (in to out). This latter bi-ionic gradient potential reverses to a value from +9 to +20 mV when monensin is present in the organic liquid mixture. Thus, the model can be build stepwise, i.e., all factors leading to the development of diffusion potentials can be introduced sequentially, helping students to understand the quantitative relationships of ionic gradients and differential membrane permeability in the generation of cell electrical signals.
Reduction of non-specific adsorption of drugs to plastic containers used in bioassays or analyses.
Fukazawa, Tominaga; Yamazaki, Yuri; Miyamoto, Yohei
2010-01-01
Non-specific adsorption (NSA) of drugs to plastic or glass containers used in clinical use is well known, but methods for reducing NSA have been rarely reported. We assessed the NSA to various containers and then investigated methods to reduce NSA. Probe drugs (methotrexate, warfarin, chloroquine, propranolol, verapamil, digoxin and paclitaxel) dissolved in water were incubated in conventional or low-adsorption containers for 4h at 4 degrees C and the NSA was determined by HPLC. They were also dissolved in aqueous methanol or acetonitrile and the NSA to a conventional polypropylene microplate was determined. Finally, tissue culture microplates were coated with silane coupling agents and the effects of the coatings were evaluated. Hydrophobic drugs (paclitaxel, verapamil and digoxin) were highly adsorbed to conventional plastic microplates, but in addition to hydrophobic drugs, positively charged drugs were well adsorbed to the tissue culture microplate. Low-adsorption microplates could reduce NSA below 15%, but positively charged or neutral hydrophobic drugs showed relatively higher adsorption. Acetonitrile showed stronger NSA inhibition than that of methanol, but the peak shapes of methotrexate and chloroquine were broadened and split. Among the silane coupling agents, GPTMS suppressed the NSA below 10%. Also, AATMS resembled the NSA pattern of GPTMS, but it increased the adsorption of methotrexate to 29%. On conventional plastic microplates, NSA is mainly driven by hydrophobic interactions, but on tissue culture microplates and low-adsorption microplates, in addition to hydrophobic interactions, ionic interactions play a role in the NSA. Therefore, to reduce the NSA to plastic containers, both hydrophobic and ionic interactions should be reduced using amphiphilic organic solvents or neutral and hydrophilic coatings. 2010 Elsevier Inc. All rights reserved.
NASA Astrophysics Data System (ADS)
Acree, William; Chickos, James S.
2017-03-01
The second part of this compendium concludes with a collection of phase change enthalpies of organic molecules inclusive of C11-C192 reported over the period 1880-2015. Also included are phase change enthalpies including fusion, vaporization, and sublimation enthalpies for organometallic, ionic liquids, and a few inorganic compounds. Paper I of this compendium, published separately, includes organic compounds from C1 to C10 and describes a group additivity method for evaluating solid, liquid, and gas phase heat capacities as well as temperature adjustments of phase changes. Paper II of this compendium also includes an updated version of a group additivity method for evaluating total phase change entropies which together with the fusion temperature can be useful in estimating total phase change enthalpies. Other uses include application in identifying potential substances that either form liquid or plastic crystals or exhibit additional phase changes such as undetected solid-solid transitions or behave anisotropically in the liquid state.
Lodge, Timothy P; Ueki, Takeshi
2016-01-01
Room temperature ionic liquids are of great interest for many advanced applications, due to the combination of attractive physical properties with essentially unlimited tunability of chemical structure. High chemical and thermal stability, favorable ionic conductivity, and complete nonvolatility are just some of the most important physical characteristics that make ionic liquids promising candidates for emerging technologies. Examples include separation membranes, actuators, polymer gel electrolytes, supercapacitors, ion batteries, fuel cell membranes, sensors, printable plastic electronics, and flexible displays. However, in these and other applications, it is essential to solidify the ionic liquid, while retaining the liquid state properties of interest. A broadly applicable solidification strategy relies on gelation by addition of suitable triblock copolymers with the ABA architecture, producing ion gels or ionogels. In this paradigm, the A end blocks are immiscible with the ionic liquid, and consequently self-assemble into micellar cores, while some fraction of the well-solvated B midblocks bridge between micelles, forming a percolating network. The chemical structures of the A and B repeat units, the molar mass of the blocks, and the concentration of the copolymer in the ionic liquid are all independently tunable to attain desired property combinations. In particular, the modulus of the resulting ion gel can be readily varied between 100 Pa and 1 MPa, with little sacrifice of the transport properties of the ionic liquid, such as ionic conductivity or gas diffusivity. Suitable A blocks can impart thermoreversible gelation (with solidification either on heating or cooling) or even photoreversible gelation. By virtue of the nonvolatility of ionic liquids, a wide range of processing strategies can be employed directly to prepare ion gels in thin or thick film forms, including solvent casting, spin coating, aerosol jet printing, photopatterning, and transfer printing. For higher modulus ion gels it is even possible to employ a manual "cut and stick" strategy for easy device fabrication. Ion gels prepared from common triblock copolymers, for example, with A = polystyrene and B = poly(ethylene oxide) or poly(methyl methacrylate), in imidazolium based ionic liquids provide exceptional performance in membranes for separating CO 2 from N 2 or CH 4 . The same materials also are the best available gate dielectrics for printed plastic electronics, because their high capacitance endows organic transistors with milliamp output currents for sub-1 V applied bias, with switching speeds that can go well beyond 100 kHz, while being amenable to large area roll-to-roll printing. Incorporation of well-designed electroluminescent (e.g., Ru(bpy) 3 -based) or electrochromic (e.g., viologen-based) moieties into ion gels held between transparent electrodes yields flexible color displays operating with sub-1 V dc inputs.
Long alkyl-chain imidazolium ionic liquids: Antibiofilm activity against phototrophic biofilms.
Reddy, G Kiran Kumar; Nancharaiah, Y V; Venugopalan, V P
2017-07-01
Biofilm formation is problematic and hence undesirable in medical and industrial settings. In addition to bacteria, phototrophic organisms are an integral component of biofilms that develop on surfaces immersed in natural waters. 1-Alkyl-3-methyl imidazolium ionic liquids (IL) with varying alkyl chain length were evaluated for their influence on the formation of monospecies (Navicula sp.) and multispecies biofilms under phototrophic conditions. An IL with a long alkyl side chain, 1-hexadecyl-3-methylimidaazolium chloride ([C 16 (MIM)][Cl]) retarded growth, adhesion and biofilm formation of Navicula sp. at concentrations as low as 5μM. Interestingly, [C 16 (MIM)][Cl] was very effective in preventing multispecies phototrophic biofilms on fibre reinforced plastic surfaces immersed in natural waters (fresh and seawater). SYTOX ® Green staining and chlorophyll leakage assay confirmed that the biocidal activity of the IL was exerted through cell membrane disruption. The data show that [C 16 (MIM)][Cl] is a potent inhibitor of phototrophic biofilms at micromolar concentrations and a promising agent for biofilm control in re-circulating cooling water systems. This is the first report that ionic liquids inhibit biofilm formation by phototrophic organisms which are important members of biofilms in streams and cooling towers. Copyright © 2017 Elsevier B.V. All rights reserved.
Toba, Faustino A.; Visai, Livia; Trivedi, Sheetal; Lowy, Franklin D.
2012-01-01
Staphylococcus epidermidis infections are common complications of prosthetic device implantation. SdrF, a surface protein, appears to play a critical role in the initial colonization step by adhering to type I collagen and Dacron™. The role of ionic interactions in S. epidermidis adherence to prosthetic material was examined. SdrF was cloned and expressed in Lactococcus lactis. The effect of pH, cation concentration and detergents on adherence to different types of plastic surfaces was assessed by crystal violet staining and bacterial cell counting. SdrF, in contrast with controls and other S. epidermidis surface proteins, bound to hydrophobic materials such as polystyrene. Binding was an ionic interaction and was affected by surface charge of the plastic, pH and cation concentration. Adherence of the SdrF construct was increased to positively charged plastics and was reduced by increasing concentrations of Ca2+ and Na+. Binding was optimal at pH 7.4. Kinetic studies demonstrated that the SdrF B domain, as well as one of the B subdomains was sufficient to mediate binding. The SdrF construct also bound more avidly to Goretex™ than the lacotococcal control. SdrF is a multifunctional protein that contributes to prosthetic devices infections by ionic, as well as specific receptor-ligand interactions. PMID:23039791
NASA Astrophysics Data System (ADS)
Pitawala, H. M. J. C.; Dissanayake, M. A. K. L.; Seneviratne, V. A.
2006-06-01
Poly (ethylene oxide)-(PEO)-based composite polymer electrolytes are of great interest for solid-state-electrochemical devices. This paper presents the results of a preliminary study on electrical conductivity and thermal behavior (DSC) of composite polymer electrolytes (CPEs) containing PEO: LiCF3SO3 complexed with plasticizer (EC) and incorporating nano-sized particles of the ceramic filler Al2O3. Ionic conductivity enhancement in these electrolytes has been obtained by optimizing the combined effect of the plasticizer and the ceramic filler. Nano-composite, plasticized polymer electrolyte films (400-600μm) were prepared by common solvent casting method. It was revealed that the presence of the Al2O3 filler in PEO: LiTf polymer electrolyte significantly enhanced the ionic conductivity in the temperature range of interest, giving the maximum conductivity for (PEO)9LiTf+15 wt.% Al2O3 CPE [σRT (max)=2×10-5 S cm-1]. It was also observed that the addition of plasticizer (EC) to this electrolyte up to a concentration of 50 wt. % EC, showed a further conductivity enhancement [σRT (max) = 1.5×10-4 S cm-1]. It is suggested that the conductivity is enhanced mainly by two mechanisms. The plasticizer (EC) would directly contribute by reducing the crystallinity and increasing the amorphous phase content of the polymer electrolytes. The ceramic filler (Al2O3) would contribute to conductivity enhancement by creating additional sites to migrating ionic species through transient bonding with O/OH groups in the filler surface. The decrease of Tg values of plasticized CPE systems seen in the DSC thermograms points towards the improved segmental flexibility of polymer chains, increasing the mobility of conducting ions.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Chew, K. W.; Tan, C. G.; Osman, Z.
The effects of plasticizer and lithium salt on PMMA-based solid polymer electrolyte have been investigated. In current project, three system samples consisted of pure poly(methyl methacrylate (PMMA) system, plasticized poly(methyl methacrylate)(PMMA-EC) system and the LiCF{sub 3}SO{sub 3} salted-poly(methyl methacrylate) containing a fixed amount of plasticizer ([PMMA-EC]-LiCF{sub 3}SO{sub 3}) system have been prepared using solution casting technique. The conductivities of the films from each system are characterized by impedance spectroscopy and infrared spectrum. With the addition of plasticizer, results show improvement on the ionic conductivity value where the value of 6.25x10{sup -10} Scm{sup -1} is obtained. This may be due tomore » the nature of plasticizer that softens the polymer and hence enhanced the ionic transportation across the polymer. The room temperature conductivity for the highest conducting sample in the ([PMMA-EC]-LiCF{sub 3}SO{sub 3}) system is 1.36x10{sup -5} Scm{sup -1}. Fourier Transform Infrared Spectroscopy (FTIR) indicates complexation between the polymer and the plasticizer and the polymer, the plasticizer and the salts, and the result of XRD further supports the observation.« less
NASA Astrophysics Data System (ADS)
Kirova, Natasha; Brazovskii, Serguei
2014-03-01
Ferroelectricity is a rising demand in fundamental and applied solid state physics. Ferroelectrics are used in microelectronics as active gate materials, in capacitors, electro-optical-acoustic modulators, etc. There is a particular demand for plastic ferroelectrics, e.g. as a sensor for acoustic imaging in medicine and beyond, in shapeable capacitors, etc. Microscopic mechanisms of ferroelectric polarization in traditional materials are typically ionic. In this talk we discuss the electronic ferroelectrics - carbon-based materials: organic crystals, conducting polymers and graphene nano-ribbons. The motion of walls, separating domains with opposite electric polarisation, can be influenced and manipulated by terahertz and infra-red range optics.
ERIC Educational Resources Information Center
Kamber, Nahrain E.; Tsujii, Yasuhito; Keets, Kate; Waymouth, Robert M.; Pratt, Russell C.; Nyce, Gregory W.; Hedrick, James L.
2010-01-01
The depolymerization of the plastic polyethylene terephthalate (PET or PETE) is described in this laboratory procedure. The transesterification reaction used to depolymerize PET employs a highly efficient N-heterocyclic carbene catalyst derived from a commercially available imidazolium ionic liquid. N-heterocyclic carbenes are potent nucleophilic…
Composite gel polymer electrolyte for lithium ion batteries
NASA Astrophysics Data System (ADS)
Naderi, Roya
Composite gel polymer electrolyte (CGPE) films, consisting of poly (vinylidene fluoride-hexafluoropropylene) (PVdF-HFP) as the membrane, DMF and PC as solvent and plasticizing agent, mixture of charge modified TiO2 and SiO 2 nano particles as ionic conductors, and LiClO4+LiPF 6 as lithium salts were fabricated. Following the work done by Li et al., CGPE was coated on an O2-plasma treated trilayer polypropylene-polyethylene-polypropylene membrane separator using solution casting technique in order to improve the adhesive properties of gel polymer electrolyte to the separator membrane and its respective ionic conductivity due to decreasing the bulk resistance. In acidic CGPE with, the mixture of acid treated TiO2 and neutral SiO2 nano particles played the role of the charge modified nano fillers with enhanced hydroxyl groups. Likely, the mixture of neutral TiO 2 nano particles with basic SiO2 prepared through the hydrolization of tetraethyl orthosilicate (TEOS) provided a more basic environment due to the residues of NH4OH (Ammonium hydroxide) catalyst. The O2 plasma treated separator was coated with the solution of PVDF-HFP: modified nano fillers: Organic solvents with the mixture ratio of 0.1:0.01:1. After the evaporation of the organic solvents, the dried coated separator was soaked in PC-LiClO4+LiPF6 in EC: DMC:DEC (4:2:4 in volume) solution (300% wt. of PVDF-HFP) to form the final CGPE. Lim et al. has reported the enhanced ionic conductivity of 9.78*10-5 Scm-1 in an acidic composite polystyrene-Al2O3 solid electrolyte system with compared to that of basic and neutral in which the ionic conductivity undergoes an ion hopping process in solid interface rather than a segmental movement of ions through the plasticized polymer chain . Half-cells with graphite anode and Li metal as reference electrode were then assembled and the electrochemical measurements and morphology examinations were successfully carried out. Half cells demonstrated a considerable change in their electrochemical performance upon the enhancement of acidic properties of the CGPE, gaining the reversible specific capacity of 314 mAh.g-1 in acidic CGPE vs. 247 mAh.g-1 in basic CGPE C/20 after 33 cycles. The CGPE exhibited submicron pore size while the ionic conductivities were in order of 10-3 and 10-5 Scm-1 with and without modified nano-fillers respectively.
NASA Technical Reports Server (NTRS)
Young, L. R.
1976-01-01
Progress in the development of a cohesive theory of the underlying physiological mechanisms associated with spatial orientation in unusual environments is described. Results can be applied to providing means of preventing and/or minimizing the space motion sickness which has been observed during prolonged space missions. Three major areas were investigated: (1) the interaction of visual and vestibular cues in conflict in the human, (2) the plasticity of the vestibulo-ocular reflex in monkeys, and (3) end organ function in the ray with particular emphasis on the effect of ionic concentration.
Yokota, Yasuyuki; Miyamoto, Hiroo; Imanishi, Akihito; Takeya, Jun; Inagaki, Kouji; Morikawa, Yoshitada; Fukui, Ken-Ichi
2018-05-09
Electric double-layer transistors based on ionic liquid/organic semiconductor interfaces have been extensively studied during the past decade because of their high carrier densities at low operation voltages. Microscopic structures and the dynamics of ionic liquids likely determine the device performance; however, knowledge of these is limited by a lack of appropriate experimental tools. In this study, we investigated ionic liquid/organic semiconductor interfaces using molecular dynamics to reveal the microscopic properties of ionic liquids. The organic semiconductors include pentacene, rubrene, fullerene, and 7,7,8,8-tetracyanoquinodimethane (TCNQ). While ionic liquids close to the substrate always form the specific layered structures, the surface properties of organic semiconductors drastically alter the ionic dynamics. Ionic liquids at the fullerene interface behave as a two-dimensional ionic crystal because of the energy gain derived from the favorable electrostatic interaction on the corrugated periodic substrate.
Zhou, Yundong; Wang, Xiaoen; Zhu, Haijin; Yoshizawa-Fujita, Masahiro; Miyachi, Yukari; Armand, Michel; Forsyth, Maria; Greene, George W; Pringle, Jennifer M; Howlett, Patrick C
2017-08-10
Organic ionic plastic crystals (OIPCs) are a class of solid-state electrolytes with good thermal stability, non-flammability, non-volatility, and good electrochemical stability. When prepared in a composite with electrospun polyvinylidene fluoride (PVdF) nanofibers, a 1:1 mixture of the OIPC N-ethyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide ([C 2 mpyr][FSI]) and lithium bis(fluorosulfonyl)imide (LiFSI) produced a free-standing, robust solid-state electrolyte. These high-concentration Li-containing electrolyte membranes had a transference number of 0.37(±0.02) and supported stable lithium symmetric-cell cycling at a current density of 0.13 mA cm -2 . The effect of incorporating PVdF in the Li-containing plastic crystal was investigated for different ratios of PVdF and [Li][FSI]/[C 2 mpyr][FSI]. In addition, Li|LiNi 1/3 Co 1/3 Mn 1/3 O 2 cells were prepared and cycled at ambient temperature and displayed a good rate performance and stability. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Nguyen, Chien A; Xiong, Shanxin; Ma, Jan; Lu, Xuehong; Lee, Pooi See
2011-08-07
Solid polymer electrolytes with excellent ionic conductivity (above 10(-4) S cm(-1)), which result in high optical modulation for solid electrochromic (EC) devices are presented. The combination of a polar host matrix poly(vinylidene fluoride-trifluoroethylene) P(VDF-TrFE) and a solid plasticized of a low molecular weight poly(ethylene oxide) (PEO) (M(w)≤ 20,000) blended polymer electrolyte serves to enhance both the dissolution of lithium salt and the ionic transport. Calorimetric measurement shows a reduced crystallization due to a better intermixing of the polymers with small molecular weight PEO. Vibrational spectroscopy identifies the presence of free ions and ion pairs in the electrolytes with PEO of M(w)≤ 8000. The ionic dissolution is improved using PEO as a plasticizer when compared to liquid propylene carbonate, evidently shown in the transference number analysis. Ionic transport follows the Arrhenius equation with a low activation energy (0.16-0.2 eV), leading to high ionic conductivities. Solid electrochromic devices fabricated with the blended P(VDF-TrFE)/PEO electrolytes and polyaniline show good spectroelectrochemical performance in the visible (300-800 nm) and near-infrared (0.9-2.4 μm) regions with a modulation up to 60% and fast switching speed of below 20 seconds. The successful introduction of the solid polymer electrolytes with its best harnessed qualities helps to expedite the application of various electrochemical devices. This journal is © the Owner Societies 2011
Effect of Al2O3 nanoparticles in plasticized PMMA-LiClO4 based solid polymer electrolyte
NASA Astrophysics Data System (ADS)
Pal, P.; Ghosh, A.
2017-05-01
We have studied the broadband complex conductivity spectra covering a 0.01 Hz-3 GHz frequency range for plasticized PMMA-LiClO4 based solid polymer electrolyte embedded with Al2O3 nanoparticle. We have analyzed the conductivity spectra using the random free-energy barrier model (RBM) coupled with electrode polarization contribution in the low frequency region and at high temperatures. The temperature dependence of the ionic conductivity obtained from the analysis has been analyzed using Vogel-Tammann-Fulcher equation. The maximum ionic conductivity ˜ 1.93×10-4 S/cm has been obtained for 1 wt% Al2O3 nanoparticle.
Antifungal activity of ionic liquids based on (-)-menthol: a mechanism study.
Suchodolski, Jakub; Feder-Kubis, Joanna; Krasowska, Anna
2017-04-01
The mechanism of toxicity of chiral ionic liquids with (1R,2S,5R)-(-)-menthol [C n -Am-Men][Cl] (n=10, 11 or 12) in the fungus Candida albicans is reported here. Ionic liquids were more toxic towards Candida strain lacking all identified multidrug resistance efflux pumps. Moreover, the compounds tested inhibited C. albicans filamentation at the concentration at which detached fungal cells also adhered to the plastic surface. Our results showed the high activity of all the tested chiral ionic liquids in the permeabilization of C. albicans' membranes and in the digestion and interruption of the cell wall. The investigated ionic liquids thus have potential as disinfectants because besides their antifungal and antiadhesive action these compounds do not cause hemolysis. Copyright © 2017 Elsevier GmbH. All rights reserved.
Cacho, Juan Ignacio; Campillo, Natalia; Viñas, Pilar; Hernández-Córdoba, Manuel
2017-03-01
A new procedure is proposed for the analysis of migration test solutions obtained from plastic bottles used in the packaging of edible oils. Ultrasound-assisted emulsification microextraction with ionic liquids was applied for the preconcentration of six phthalate esters: dimethylphthalate, diethylphthalate, di-n-butylphthalate, n-butylbenzylphthalate, di-2-ethylhexylphthalate, and di-n-octylphthalate. The enriched ionic liquid was directly analyzed by gas chromatography and mass spectrometry using direct insert microvial thermal desorption. The different factors affecting the microextraction efficiency, such as volume of the extracting phase (30 μL of the ionic liquid) and ultrasound application time (25 s), and the thermal desorption step, such as desorption temperature and time, and gas flow rate, were studied. Under the selected conditions, detection limits for the analytes were in the 0.012-0.18 μg/L range, while recovery assays provided values ranging from 80 to 112%. The use of butyl benzoate as internal standard increased the reproducibility of the analytical procedure. When the release of the six phthalate esters from the tested plastic bottles to liquid simulants was monitored using the optimized procedure, analyte concentrations of between 1.0 and 273 μg/L were detected. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Methods of using ionic liquids having a fluoride anion as solvents
Pagoria, Philip [Livermore, CA; Maiti, Amitesh [San Ramon, CA; Gash, Alexander [Brentwood, CA; Han, Thomas Yong [Pleasanton, CA; Orme, Christine [Oakland, CA; Fried, Laurence [Livermore, CA
2011-12-06
A method in one embodiment includes contacting a strongly hydrogen bonded organic material with an ionic liquid having a fluoride anion for solubilizing the strongly hydrogen bonded organic material; and maintaining the ionic liquid at a temperature of about 90.degree. C. or less during the contacting. A method in another embodiment includes contacting a strongly hydrogen bonded organic material with an ionic liquid having an acetate or formate anion for solubilizing the strongly hydrogen bonded organic material; and maintaining the ionic liquid at a temperature of less than about 90.degree. C. during the contacting.
CT contrast extravasation in the upper extremity: strategies for management.
Sbitany, Hani; Koltz, Peter F; Mays, Chester; Girotto, John A; Langstein, Howard N
2010-01-01
Extravasation of CT scan contrast media into upper extremity subcutaneous tissue is a relatively frequent complication of injection. Potential sequelae of extravasation include compartment syndrome, skin sloughing, and necrosis. Many institutions institute protocols requiring inpatient plastic surgery consultations immediately following extravasation injury to the upper extremity. We hypothesize that conversion to non-ionic contrast media for contrast CT studies has greatly reduced the incidence of severe extravasation injuries, and may alleviate the need for routine hand surgery consultations. Records from 102 consecutive CT contrast media extravasation injuries were identified. Data acquired from a single institution included type and amount of contrast extravasated, anatomic location, post-procedural clinical symptoms, whether consult was obtained, and final recommendations and outcome. In 102 consecutive cases, immediate surgical therapy was necessary in 0. Non-ionic medium was used in 94% of these cases, and ionic dye was used in 6%. Extravasation of less than 100 cc occurred in 90%, and only 10% were greater. Plastic surgery consultation was immediately obtained in 42% of cases. Factors prompting consultation included extravasation >30 cc, and the presence of erythema or induration. Trends for consultation remained without discernable pattern when patients were stratified by age, amount of extravasate, or anatomic location. Conservative management was recommended in all cases. This included elevation of the extremity, frequent pulse and sensation exams, local message, and temporary splinting. There were no secondary complications requiring surgical intervention. Extravasation of non-ionic CT contrast media appears to be innocuous and can be treated with conservative therapy. Plastic surgery consultation should be obtained when there are obvious signs of skin and soft tissue compromise or symptoms of compartment syndrome. Copyright 2010 Surgical Associates Ltd. Published by Elsevier Ltd. All rights reserved.
Novel polymer electrolytes based on cationic polyurethane with different alkyl chain length
NASA Astrophysics Data System (ADS)
Liu, Libin; Wu, Xiwen; Li, Tianduo
2014-03-01
A series of comb-like cationic polyurethanes (PUs) were synthesized by quaternizing different bromoalkane (C2H5Br, C8H17Br, and C14H29Br) with polyurethane. Solid polymer electrolytes were prepared by complexes cationic PUs with different content of LiClO4. All the solid polymer electrolytes had sufficient thermal stability as confirmed by TGA and exhibited a single-phase behavior evidenced by DSC results. For these electrolytes, FT-IR spectra indicated the formation of polymer-ion complexes. The ac impedance spectra show that the conductivity of the electrolytes follow the Arrhenius behavior, and ionic conductivity is associated with both the charge migration of ions between coordination sites and transmission between aggregates, as confirmed by FT-IR and SEM. Alkyl quaternary ammonium salts in the polymer backbone are recognized as inherent plasticizers, which make the electrolytes exhibit liquid-like behavior. The plasticizing effect of PU-C8 and PU-C14 electrolytes are more effective than that of PU-C2 electrolyte. Maximum ionic conductivity at room temperature for PU-C8 electrolytes containing 50 wt% LiClO4 reached 1.1 × 10-4 S cm-1. This work provides a new research clue that alkyl quaternary ammonium salts could be used as inherent plasticizers and hence make the system behave like a liquid with high ionic conductivity, while preserving the dimensional stability of the solids.
Low Temperature Magnetic Ordering of the Magnetic Ionic Plastic Crystal, Choline[FeCl4
NASA Astrophysics Data System (ADS)
de Pedro, I.; García-Saiz, A.; Andreica, D.; Fernández Barquín, L.; Fernández-Díaz, M. T.; Blanco, J. A.; Amato, A.; Rodríguez Fernández, J.
2015-11-01
We report on the nature of the low temperature magnetic ordering of a magnetic ionic plastic crystal, Choline[FeCl4]. This investigation was carried out using heat capacity measurements, neutron diffraction experiments and muon spin relaxation (μSR) spectroscopy. The calorimetric measurements show the onset of an unusual magnetic ordering below 4 K with a possible second magnetic phase transition below 2 K. Low temperature neutron diffraction data reveal a three dimensional antiferromagnetic ordering at 2 K compatible with the previous magnetometry results. The analysis of μSR spectra indicates a magnetic phase transition below 2.2 K. At 1.6 K, the analysis of the shape of the μSR spectra suggests the existence of an additional magnetic phase with features of a possible incommensurate magnetic structure.
NASA Technical Reports Server (NTRS)
Meador, Mary Ann B.; Kinder, James D.; Bennett, William R.
2002-01-01
Lithium-based polymer batteries for aerospace applications need the ability to operate in temperatures ranging from -70 to 70 C. Current state-of-the-art solid polymer electrolytes (based on amorphous polyethylene oxide, PEO) have acceptable ionic conductivities (10-4 to 10-3 S/cm) only above 60 C. Higher conductivity can be achieved in the current systems by adding solvent or plasticizers to the solid polymer to improve ion transport. However, this can compromise the dimensional and thermal stability of the electrolyte, as well as compatibility with electrode materials. One of NASA Glenn Research Center's objectives in the PERS program is to develop new electrolytes having unique molecular architectures and/or novel ion transport mechanisms, leading to good ionic conductivity at room temperature and below without solvents or plasticizers.
Cacho, Juan Ignacio; Campillo, Natalia; Viñas, Pilar; Hernández-Córdoba, Manuel
2016-01-01
A new procedure based on direct insert microvial thermal desorption injection allows the direct analysis of ionic liquid extracts by gas chromatography and mass spectrometry (GC-MS). For this purpose, an in situ ionic liquid dispersive liquid-liquid microextraction (in situ IL DLLME) has been developed for the quantification of bisphenol A (BPA), bisphenol Z (BPZ) and bisphenol F (BPF). Different parameters affecting the extraction efficiency of the microextraction technique and the thermal desorption step were studied. The optimized procedure, determining the analytes as acetyl derivatives, provided detection limits of 26, 18 and 19 ng L(-1) for BPA, BPZ and BPF, respectively. The release of the three analytes from plastic containers was monitored using this newly developed analytical method. Analysis of the migration test solutions for 15 different plastic containers in daily use identified the presence of the analytes at concentrations ranging between 0.07 and 37 μg L(-1) in six of the samples studied, BPA being the most commonly found and at higher concentrations than the other analytes.
Grau, James W; Huang, Yung-Jen
2018-04-07
Evidence is reviewed that behavioral training and neural injury can engage metaplastic processes that regulate adaptive potential. This issue is explored within a model system that examines how training affects the capacity to learn within the lower (lumbosacral) spinal cord. Response-contingent (controllable) stimulation applied caudal to a spinal transection induces a behavioral modification indicative of learning. This behavioral change is not observed in animals that receive stimulation in an uncontrollable manner. Exposure to uncontrollable stimulation also engages a process that disables spinal learning for 24-48 h. Controllable stimulation has the opposite effect; it engages a process that enables learning and prevents/reverses the learning deficit induced by uncontrollable stimulation. These observations suggest that a learning episode can impact the capacity to learn in future situations, providing an example of behavioral metaplasticity. The protective/restorative effect of controllable stimulation has been linked to an up-regulation of brain-derived neurotrophic factor (BDNF). The disruption of learning has been linked to the sensitization of pain (nociceptive) circuits, which is enabled by a reduction in GABA-dependent inhibition. After spinal cord injury (SCI), the co-transporter (KCC2) that regulates the outward flow of Cl - is down-regulated. This causes the intracellular concentration of Cl - to increase, reducing (and potentially reversing) the inward flow of Cl - through the GABA-A receptor. The shift in GABA function (ionic plasticity) increases neural excitability caudal to injury and sets the stage for nociceptive sensitization. The injury-induced shift in KCC2 is related to the loss of descending serotonergic (5HT) fibers that regulate plasticity within the spinal cord dorsal horn through the 5HT-1A receptor. Evidence is presented that these alterations in spinal plasticity impact pain in a brain-dependent task (place conditioning). The findings suggest that ionic plasticity can affect learning potential, shifting a neural circuit from dampened/hard-wired to excitable/plastic. Copyright © 2018 Elsevier Inc. All rights reserved.
On the chemical stabilities of ionic liquids.
Sowmiah, Subbiah; Srinivasadesikan, Venkatesan; Tseng, Ming-Chung; Chu, Yen-Ho
2009-09-25
Ionic liquids are novel solvents of interest as greener alternatives to conventional organic solvents aimed at facilitating sustainable chemistry. As a consequence of their unusual physical properties, reusability, and eco-friendly nature, ionic liquids have attracted the attention of organic chemists. Numerous reports have revealed that many catalysts and reagents were supported in the ionic liquid phase, resulting in enhanced reactivity and selectivity in various important reaction transformations. However, synthetic chemists cannot ignore the stability data and intermolecular interactions, or even reactions that are directly applicable to organic reactions in ionic liquids. It is becoming evident from the increasing number of reports on use of ionic liquids as solvents, catalysts, and reagents in organic synthesis that they are not totally inert under many reaction conditions. While in some cases, their unexpected reactivity has proven fortuitously advantageous in others is has been a problem, it is imperative that when selecting an ionic liquid for a particular synthetic application, attention be paid to its compatibility with the reaction conditions. Even though, more than 200 room temperature ionic liquids are known, only a few reports have commented their effects on reaction mechanisms or rate/stability. Therefore, rather than attempting to give a comprehensive overview of ionic liquid chemistry, this review focuses on the non-innocent nature of ionic liquids, with a decided emphasis to clearly illuminate the ability of ionic liquids to affect the mechanistic aspects of some organic reactions thereby affecting and promoting the yield and selectivity.
The Plasma and Suprathermal Ion Composition (PLASTIC) Investigation on the STEREO Observatories
NASA Astrophysics Data System (ADS)
Galvin, A. B.; Kistler, L. M.; Popecki, M. A.; Farrugia, C. J.; Simunac, K. D. C.; Ellis, L.; Möbius, E.; Lee, M. A.; Boehm, M.; Carroll, J.; Crawshaw, A.; Conti, M.; Demaine, P.; Ellis, S.; Gaidos, J. A.; Googins, J.; Granoff, M.; Gustafson, A.; Heirtzler, D.; King, B.; Knauss, U.; Levasseur, J.; Longworth, S.; Singer, K.; Turco, S.; Vachon, P.; Vosbury, M.; Widholm, M.; Blush, L. M.; Karrer, R.; Bochsler, P.; Daoudi, H.; Etter, A.; Fischer, J.; Jost, J.; Opitz, A.; Sigrist, M.; Wurz, P.; Klecker, B.; Ertl, M.; Seidenschwang, E.; Wimmer-Schweingruber, R. F.; Koeten, M.; Thompson, B.; Steinfeld, D.
2008-04-01
The Plasma and Suprathermal Ion Composition (PLASTIC) investigation provides the in situ solar wind and low energy heliospheric ion measurements for the NASA Solar Terrestrial Relations Observatory Mission, which consists of two spacecraft (STEREO-A, STEREO-B). PLASTIC-A and PLASTIC-B are identical. Each PLASTIC is a time-of-flight/energy mass spectrometer designed to determine the elemental composition, ionic charge states, and bulk flow parameters of major solar wind ions in the mass range from hydrogen to iron. PLASTIC has nearly complete angular coverage in the ecliptic plane and an energy range from ˜0.3 to 80 keV/e, from which the distribution functions of suprathermal ions, including those ions created in pick-up and local shock acceleration processes, are also provided.
Lahiri, Abhishek; Li, Guozhu; Olschewski, Mark; Endres, Frank
2016-12-14
Ionic liquid-organic solvent mixtures have recently been investigated as potential battery electrolytes. However, contradictory results with these mixtures have been shown for battery performance. In this manuscript, we studied the influence of the addition of polar organic solvents into the ionic liquid electrolyte 1 M lithium bis(fluorosulfonyl)amide (LiFSI)-1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)amide ([Py 1,4 ]FSI) and tested it for lithium ion battery applications. From infrared and Raman spectroscopy, clear changes in the lithium solvation and cation-anion interactions in the ionic liquid were observed on addition of organic solvents. From the lithiation/delithiation studies on electrodeposited Ge, the storage capacity for the ionic liquid-highly polar organic solvent (acetonitrile) mixture was found to be the highest at low C-rates (0.425 C) compared to using an ionic liquid alone and ionic liquid-less polar solvent (dimethyl carbonate) mixtures. Furthermore, XPS and AFM were used to evaluate the solid electrolyte interphase (SEI) and to correlate its stability with Li storage capacity.
Nanoparticles in ionic liquids: interactions and organization.
He, Zhiqi; Alexandridis, Paschalis
2015-07-28
Ionic liquids (ILs), defined as low-melting organic salts, are a novel class of compounds with unique properties and a combinatorially great chemical diversity. Ionic liquids are utilized as synthesis and dispersion media for nanoparticles as well as for surface functionalization. Ionic liquid and nanoparticle hybrid systems are governed by a combined effect of several intermolecular interactions between their constituents. For each interaction, including van der Waals, electrostatic, structural, solvophobic, steric, and hydrogen bonding, the characterization and quantitative calculation methods together with factors affecting these interactions are reviewed here. Various self-organized structures based on nanoparticles in ionic liquids are generated as a result of a balance of these intermolecular interactions. These structures, including colloidal glasses and gels, lyotropic liquid crystals, nanoparticle-stabilized ionic liquid-containing emulsions, ionic liquid surface-functionalized nanoparticles, and nanoscale ionic materials, possess properties of both ionic liquids and nanoparticles, which render them useful as novel materials especially in electrochemical and catalysis applications. This review of the interactions within nanoparticle dispersions in ionic liquids and of the structure of nanoparticle and ionic liquid hybrids provides guidance on the rational design of novel ionic liquid-based materials, enabling applications in broad areas.
Pang, Jinhui; Liu, Xin; Zhang, Xueming; Wu, Yuying; Sun, Runcang
2013-01-01
More and more attention has been paid to environmentally friendly bio-based renewable materials as the substitution of fossil-based materials, due to the increasing environmental concerns. In this study, regenerated cellulose films with enhanced mechanical property were prepared via incorporating different plasticizers using ionic liquid 1-allyl-3-methylimidazolium chloride (AmimCl) as the solvent. The characteristics of the cellulose films were investigated by scanning electron microscopy (SEM), atomic force microscopy (AFM), thermal analysis (TG), X-ray diffraction (XRD), 13C Solid-state cross-polarization/magic angle spinning nuclear magnetic resonance (CP/MAS NMR) and tensile testing. The results showed that the cellulose films exhibited a homogeneous and smooth surface structure. It was noted that the thermal stability of the regenerated cellulose film plasticized with glycerol was increased compared with other regenerated cellulose films. Furthermore, the incorporation of plasticizers dramatically strengthened the tensile strength and improved the hydrophobicity of cellulose films, as compared to the control sample. Therefore, these notable results exhibited the potential utilization in producing environmentally friendly cellulose films with high performance properties. PMID:28809209
Evaluation of ionic liquid epoxy carbon fiber composites in a cryogenic environment
NASA Astrophysics Data System (ADS)
Lyne, Christopher T.; Henry, Christopher R.; Kaukler, William F.; Grugel, R. N.
2018-03-01
A novel ionic liquid epoxy (ILE) was used to fabricate carbon fiber composite discs which were then subjected to biaxial strain testing in liquid nitrogen. The ILE composite showed a greater strain-to-failure at cryogenic temperatures when compared to a commercial epoxy. This result is likely an effect, as shown in micrographs, of the strong ILE bonding with the carbon fibers as well as it exhibiting plastic deformation at the fracture surface.
Plasticizing Effects of Polyamines in Protein-Based Films
Sabbah, Mohammed; Di Pierro, Prospero; Giosafatto, C. Valeria L.; Esposito, Marilena; Mariniello, Loredana; Regalado-Gonzales, Carlos; Porta, Raffaele
2017-01-01
Zeta potential and nanoparticle size were determined on film forming solutions of native and heat-denatured proteins of bitter vetch as a function of pH and of different concentrations of the polyamines spermidine and spermine, both in the absence and presence of the plasticizer glycerol. Our results showed that both polyamines decreased the negative zeta potential of all samples under pH 8.0 as a consequence of their ionic interaction with proteins. At the same time, they enhanced the dimension of nanoparticles under pH 8.0 as a result of macromolecular aggregations. By using native protein solutions, handleable films were obtained only from samples containing either a minimum of 33 mM glycerol or 4 mM spermidine, or both compounds together at lower glycerol concentrations. However, 2 mM spermidine was sufficient to obtain handleable film by using heat-treated samples without glycerol. Conversely, brittle materials were obtained by spermine alone, thus indicating that only spermidine was able to act as an ionic plasticizer. Lastly, both polyamines, mainly spermine, were found able to act as “glycerol-like” plasticizers at concentrations higher than 5 mM under experimental conditions at which their amino groups are undissociated. Our findings open new perspectives in obtaining protein-based films by using aliphatic polycations as components. PMID:28489025
John, Rohit Abraham; Ko, Jieun; Kulkarni, Mohit R; Tiwari, Naveen; Chien, Nguyen Anh; Ing, Ng Geok; Leong, Wei Lin; Mathews, Nripan
2017-08-01
Emulation of biological synapses is necessary for future brain-inspired neuromorphic computational systems that could look beyond the standard von Neuman architecture. Here, artificial synapses based on ionic-electronic hybrid oxide-based transistors on rigid and flexible substrates are demonstrated. The flexible transistors reported here depict a high field-effect mobility of ≈9 cm 2 V -1 s -1 with good mechanical performance. Comprehensive learning abilities/synaptic rules like paired-pulse facilitation, excitatory and inhibitory postsynaptic currents, spike-time-dependent plasticity, consolidation, superlinear amplification, and dynamic logic are successfully established depicting concurrent processing and memory functionalities with spatiotemporal correlation. The results present a fully solution processable approach to fabricate artificial synapses for next-generation transparent neural circuits. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Dual Ionic and Organic Nature of Ionic Liquids
Shi, Rui; Wang, Yanting
2016-01-01
Inherited the advantages of inorganic salts and organic solvents, ionic liquids (ILs) exhibit many superior properties allowing them promising green solvents for the future. Although it has been widely acknowledged that the unique features of ILs originate from their dual ionic and organic nature, its microscopic physical origin still remains blurry. In this work, by comparing the ion/molecule cage structures obtained from molecular dynamics simulations for seven prototypic liquids—a molten inorganic salt, four ILs, a strongly polar organic solvent, and a weakly polar organic solvent, we have revealed that the depth of the cage energy landscape characterizes the ionic nature of ILs, whereas the slope and curvature of its mimimum determine the organic nature of ILs. This finding advances our understanding of ILs and thus will help their efficient utilization as well as the systematic design of novel functionalized ILs. PMID:26782660
Fox-Powell, Mark G; Cockell, Charles S
2018-01-01
Current knowledge of life in hypersaline habitats is mostly limited to sodium and chloride-dominated environments. This narrow compositional window does not reflect the diversity of brine environments that exist naturally on Earth and other planetary bodies. Understanding the limits of the microbial biosphere and predicting extraterrestrial habitability demands a systematic effort to characterize ionic specificities of organisms from a representative range of saline habitats. Here, we investigated a strain of Marinococcus isolated from the magnesium and sulfate-dominated Basque Lakes (British Columbia, Canada). This organism was the sole isolate obtained after exposure to exceptionally high levels of Mg 2+ and SO 4 2- ions (2.369 and 2.840 M, respectively), and grew at extremes of ionic strength not normally encountered in Na + /Cl - brines (12.141 mol liter -1 ). Its association at the 16S rDNA level with bacterial halophiles suggests that ancestral halophily has allowed it to adapt to a different saline habitat. Growth was demonstrated in media dominated by NaCl, Na 2 SO 4 , MgCl 2 , and MgSO 4 , yet despite this plasticity the strain was still restricted; requiring either Na + or Cl - to maintain short doubling times. Water activity could not explain growth rate differences between media, demonstrating the importance of ionic composition for dictating microbial growth windows. A new framework for understanding growth in brines is required, that accounts for the geochemical history of brines as well as the various stresses that ions impose on microbes. Studies such as this are required to gain a truly universal understanding of the limits of biological ion tolerance.
Sun, Xiao -Guang; Fang, Youxing; Jiang, Xueguang; ...
2015-10-22
Polymer gel electrolyte using AlCl3 complexed acrylamide as functional monomer and ionic liquids based on acidic mixture of 1-ethyl-3-methylimidazolium chloride (EMImCl) and AlCl 3 as plasticizer has been successfully prepared for the first time by free radical polymerization. Aluminum deposition is successfully obtained with a polymer gel membrane contianing 80 wt% ionic liquid. As a result, the polymer gel membranes are also good candidates for rechargeable aluminum ion batteries.
NASA Astrophysics Data System (ADS)
Pal, P.; Ghosh, A.
2016-07-01
In this paper, we have studied the dynamics and relaxation of charge carriers in poly(methylmethacrylate)-lithium salt based polymer electrolytes plasticized with ethylene carbonate. Structural and thermal properties have been examined using X-ray diffraction and differential scanning calorimetry, respectively. We have analyzed the complex conductivity spectra by using power law model coupled with the contribution of electrode polarization at low frequencies and high temperatures. The temperature dependence of the ionic conductivity and crossover frequency exhibits Vogel-Tammann-Fulcher type behavior indicating a strong coupling between the ionic and the polymer chain segmental motions. The scaling of the ac conductivity indicates that relaxation dynamics of charge carriers follows a common mechanism for all temperatures and ethylene carbonate concentrations. The analysis of the ac conductivity also shows the existence of a nearly constant loss in these polymer electrolytes at low temperatures and high frequencies. The fraction of free anions and ion pairs in polymer electrolyte have been obtained from the analysis of Fourier transform infrared spectra. It is observed that these quantities influence the behavior of the composition dependence of the ionic conductivity.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Pal, P.; Ghosh, A., E-mail: sspag@iacs.res.in
2016-07-28
In this paper, we have studied the dynamics and relaxation of charge carriers in poly(methylmethacrylate)-lithium salt based polymer electrolytes plasticized with ethylene carbonate. Structural and thermal properties have been examined using X-ray diffraction and differential scanning calorimetry, respectively. We have analyzed the complex conductivity spectra by using power law model coupled with the contribution of electrode polarization at low frequencies and high temperatures. The temperature dependence of the ionic conductivity and crossover frequency exhibits Vogel-Tammann-Fulcher type behavior indicating a strong coupling between the ionic and the polymer chain segmental motions. The scaling of the ac conductivity indicates that relaxation dynamicsmore » of charge carriers follows a common mechanism for all temperatures and ethylene carbonate concentrations. The analysis of the ac conductivity also shows the existence of a nearly constant loss in these polymer electrolytes at low temperatures and high frequencies. The fraction of free anions and ion pairs in polymer electrolyte have been obtained from the analysis of Fourier transform infrared spectra. It is observed that these quantities influence the behavior of the composition dependence of the ionic conductivity.« less
Ramesh, S; Shanti, R; Morris, Ezra
2013-01-02
Polymer electrolytes were developed by solution casting technique utilizing the materials of cellulose acetate (CA), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and deep eutectic solvent (DES). The DES is synthesized from the mixture of choline chloride and urea of 1:2 ratios. The increasing DES content well plasticizes the CA:LiTFSI:DES matrix and gradually improves the ionic conductivity and chemical integrity. The highest conducting sample was identified for the composition of CA:LiTFSI:DES (28 wt.%:12 wt.%:60 wt.%), which has the greatest ability to retain the room temperature ionic conductivity over the entire 30 days of storage time. The changes in FTIR cage peaks upon varying the DES content in CA:LiTFSI:DES prove the complexation. This complexation results in the collapse of CA matrix crystallinity, observed from the reduced intensity of XRD diffraction peaks. The DES-plasticized sample is found to be more heat-stable compared to pure CA. Nevertheless, the addition of DES diminishes the CA:LiTFSI matrix's heat-resistivity but at the minimum addition the thermal stability is enhanced. Copyright © 2012 Elsevier Ltd. All rights reserved.
Wan, Chang Jin; Liu, Yang Hui; Zhu, Li Qiang; Feng, Ping; Shi, Yi; Wan, Qing
2016-04-20
In the biological nervous system, synaptic plasticity regulation is based on the modulation of ionic fluxes, and such regulation was regarded as the fundamental mechanism underlying memory and learning. Inspired by such biological strategies, indium-gallium-zinc-oxide (IGZO) electric-double-layer (EDL) transistors gated by aqueous solutions were proposed for synaptic behavior emulations. Short-term synaptic plasticity, such as paired-pulse facilitation, high-pass filtering, and orientation tuning, was experimentally emulated in these EDL transistors. Most importantly, we found that such short-term synaptic plasticity can be effectively regulated by alcohol (ethyl alcohol) and salt (potassium chloride) additives. Our results suggest that solution gated oxide-based EDL transistors could act as the platforms for short-term synaptic plasticity emulation.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Das, S.; Ghosh, A., E-mail: sspag@iacs.res.in
We have studied ionic conductivity and dielectric permittivity of PEO-LiClO{sub 4} solid polymer electrolyte plasticized with propylene carbonate. Differential scanning calorimetry and X-ray diffraction studies confirm minimum volume fraction of crystalline phase for the polymer electrolyte with 40 wt. % propylene carbonate. The ionic conductivity exhibits a maximum for the same composition. The temperature dependence of the ionic conductivity has been well interpreted using Vogel-Tamman-Fulcher equation. Ion-ion interactions in the polymer electrolytes have been studied using Raman spectra and the concentrations of free ions, ion-pairs and ion-aggregates have been determined. The ionic conductivity increases due to the increase of freemore » ions with the increase of propylene carbonate content. But for higher content of propylene carbonate, the ionic conductivity decreases due to the increase of concentrations of ion-pairs and ion-aggregates. To get further insights into the ion dynamics, the experimental data for the complex dielectric permittivity have been studied using Havriliak–Negami function. The variation of relaxation time with temperature obtained from this formalism follows Vogel-Tamman-Fulcher equation similar to the ionic conductivity.« less
NASA Astrophysics Data System (ADS)
Sengwa, R. J.; Dhatarwal, Priyanka; Choudhary, Shobhna
2016-05-01
Solid polymer electrolyte (SPE) film consisted of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) blend matrix with lithium tetrafluroborate (LiBF4) as dopant ionic salt and poly(ethylene glycol) (PEG) as plasticizer has been prepared by solution casting method followed by melt pressing. Dielectric properties and ionic conductivity of the SPE film at different temperatures have been determined by dielectric relaxation spectroscopy. It has been observed that the dc ionic conductivity of the SPE film increases with increase of temperature and also the decrease of relaxation time. The temperature dependent relaxation time and ionic conductivity values of the electrolyte are governed by the Arrhenius relation. Correlation observed between dc conductivity and relaxation time confirms that ion transportation occurs with polymer chain segmental dynamics through hopping mechanism. The room temperature ionic conductivity is found to be 4 × 10-6 S cm-1 which suggests the suitability of the SPE film for rechargeable lithium batteries.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Sengwa, R. J., E-mail: rjsengwa@rediffmail.com; Dhatarwal, Priyanka, E-mail: dhatarwalpriyanka@gmail.com; Choudhary, Shobhna, E-mail: shobhnachoudhary@rediffmail.com
2016-05-06
Solid polymer electrolyte (SPE) film consisted of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) blend matrix with lithium tetrafluroborate (LiBF{sub 4}) as dopant ionic salt and poly(ethylene glycol) (PEG) as plasticizer has been prepared by solution casting method followed by melt pressing. Dielectric properties and ionic conductivity of the SPE film at different temperatures have been determined by dielectric relaxation spectroscopy. It has been observed that the dc ionic conductivity of the SPE film increases with increase of temperature and also the decrease of relaxation time. The temperature dependent relaxation time and ionic conductivity values of the electrolyte are governedmore » by the Arrhenius relation. Correlation observed between dc conductivity and relaxation time confirms that ion transportation occurs with polymer chain segmental dynamics through hopping mechanism. The room temperature ionic conductivity is found to be 4 × 10{sup −6} S cm{sup −1} which suggests the suitability of the SPE film for rechargeable lithium batteries.« less
NASA Astrophysics Data System (ADS)
He, Ruixuan
In pursuit of safer and more flexible solid-state lithium ion batteries, solid polymer electrolytes have emerged as a promising candidate. The present dissertation entails exploration of solid plasticized, photopolymerized (i.e. ultraviolent-cured) polymer electrolyte membranes (PEM) for fulfilling the critical requirements of electrolytes, such as high ionic conductivity and good thermal and electrochemical stability, among others. Electrochemical performance of PEMs containing lithium ion half-cells was also investigated at different two temperatures. Phase diagram approach was adopted to guide the fabrication of two types of plasticized PEMs. Prepolymer poly (ethylene glycol) diacrylate (PEGDA) was used as a matrix for building an ionic conductive and mechanically sturdy network. Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) was incorporated as a source of lithium ions, while a solid plasticizer succinonitrile (SCN) and a liquid plasticizer tetraethylene glycol dimethyl ether (TEGDME) were incorporated in the respective systems. The important role of plasticizer on the enhancement of ionic conductivity (sigma) to the superionic conductive level (10-3 S/cm) was revealed in both systems. It is worth noting that photopolymerization induced crystallization (PIC) occurred during UV-curing in the SCN-rich region of the ternary PEGDA/LiTFSI/SCN ternary mixtures. The PEM thus formed contained a plastic crystal phase, which showed lower σ relative to their amorphous PEGDA/LiTFSI/TEGDME counterpart. Comparisons on other thermal and electrochemical properties of the two types of PEMs are presented in Chapter IV. For the PEGDA/LiTFSI/SCN PEMs, fundamental study was carried out to clarify the relationship between σ and glass transition temperature (T g). In lithium salt/polymer binary PEMs, increase in Tg and reduction in σ were observed; these may be attributed to ion-dipole complexation between dissociated lithium cations and ether oxygen upon salt addition. Notably, above the threshold salt concentration of 7 mol %, dual loss tangent peaks were observed in dynamic mechanical studies. These might be ascribed to segmental relaxations of ion-dipole complexed networks and that of polymer chains surrounding the undissociated lithium salt acting like "fillers". Upon SCN incorporation, these two peaks merged into one that was further suppressed below the Tg of the pure network, whereas σ improved to the superionic conductor level. The role of SCN on the σ enhancement as both plasticizer for the polymer network and ionizer for the salt is discussed in Chapter V. In order to improve the mechanical toughness of the highly conductive PEGDA/LiTFSI/SCN PEM, effects of prepolymer molecular weight on mechanical and electrochemical properties of PEMs were further investigated. By increasing molecular weight of PEGDA from 700 to 6000 g/mol, toughness and elongation at break were enhanced as expected. Interestingly, improved ionic conductivity was achieved simultaneously. The dual improvement may be attributed to the less chemical crosslinked points and the more flexible chain motion in the looser network of PEGDA6000-PEM relative to its PEGDA700 counterpart. Subsequently, high thermal stability and electrochemical stability of both types of PEMs, as well as the satisfactory room temperature charge/discharge cycling performance of PEM containing lithium ion half-cells were observed. The pertinent information is documented in Chapter VI. Finally, the investigation of the charge/discharge cycling performance of solid-state LiFePO4 half-cells at an elevated temperature of 60°C is discussed in Chapter VII. In the half-cells, particularly, SCN plasticized PEMs with and without electrolyte modifier lithium bis(oxalato)borate (LiBOB) were respectively employed. Rapid decline of capacity and increase of cell resistance were found in the unmodified PEM containing cell; however, these deteriorations were greatly suppressed upon LiBOB modification. Electrochemical and thermal compatibility of PEMs towards different electrodes were examined in several symmetric cells and half-cells. Detailed characterization on LiFePO 4 electrodes and PEMs retrieved from these cells implied that the observed battery failure might be triggered by an amide-forming side reaction that took place at the interface of a SCN plasticized PEM and a lithium electrode at high temperature. Of particular importance is the fact that this detrimental side reaction was effectively suppressed upon LiBOB electrolyte modifier addition. Plausible mechanisms are discussed.
Diddens, Diddo; Heuer, Andreas
2014-01-30
We present an extensive molecular dynamics (MD) simulation study of the lithium ion transport in ternary polymer electrolytes consisting of poly(ethylene oxide) (PEO), lithium-bis(trifluoromethane)sulfonimide (LiTFSI), and the ionic liquid N-methyl-N-propylpyrrolidinium bis(trifluoromethane)sulfonimide (PYR13TFSI). In particular, we focus on two different strategies by which the ternary electrolytes can be devised, namely by (a) adding the ionic liquid to PEO20LiTFSI and (b) substituting the PEO chains in PEO20LiTFSI by the ionic liquid. To grasp the changes of the overall lithium transport mechanism, we employ an analytical, Rouse-based cation transport model (Maitra et al. Phys. Rev. Lett. 2007, 98, 227802), which has originally been devised for binary PEO-based electrolytes. This model distinguishes three different microscopic transport mechanisms, each quantified by an individual time scale. In the course of our analysis, we extend this mathematical description to account for an entirely new transport mechanism, namely, the TFSI-supported diffusion of lithium ions decoupled from the PEO chains, which emerges for certain stoichiometries. We find that the segmental mobility plays a decisive role in PEO-based polymer electrolytes. That is, whereas the addition of the ionic liquid to PEO20LiTFSI plasticizes the polymer network and thus also increases the lithium diffusion, the amount of free, mobile ether oxygens reduces when substituting the PEO chains by the ionic liquid, which compensates the plasticizing effect. In total, our observations allow us to formulate some general principles about the lithium ion transport mechanism in ternary polymer electrolytes. Moreover, our insights also shed light on recent experimental observations (Joost et al. Electrochim. Acta 2012, 86, 330).
Bucky gel actuators optimization towards haptic applications
NASA Astrophysics Data System (ADS)
Bubak, Grzegorz; Ansaldo, Alberto; Ceseracciu, Luca; Hata, Kenji; Ricci, Davide
2014-03-01
An ideal plastic actuator for haptic applications should generate a relatively large displacement (minimum 0.2-0.6 mm, force (~50 mN/cm2) and a fast actuation response to the applied voltage. Although many different types of flexible, plastic actuators based on electroactive polymers (EAP) are currently under investigation, the ionic EAPs are the only ones that can be operated at low voltage. This property makes them suitable for applications that require inherently safe actuators. Among the ionic EAPs, bucky gel based actuators are very promising. Bucky gel is a physical gel made by grounding imidazolium ionic liquids with carbon nanotubes, which can then be incorporated in a polymeric composite matrix to prepare the active electrode layers of linear and bending actuators. Anyhow, many conflicting factors have to be balanced to obtain required performance. In order to produce high force a large stiffness is preferable but this limits the displacement. Moreover, the bigger the active electrode the larger the force. However the thicker an actuator is, the slower the charging process becomes (it is diffusion limited). In order to increase the charging speed a thin electrolyte would be desirable, but this increases the probability of pinholes and device failure. In this paper we will present how different approaches in electrolyte and electrode preparation influence actuator performance and properties taking particularly into account the device ionic conductivity (which influences the charging speed) and the electrode surface resistance (which influences both the recruitment of the whole actuator length and its speed).
Using FT-IR Spectroscopy to Measure Charge Organization in Ionic Liquids
Burba, Christopher M.; Janzen, Jonathan; Butson, Eric D.; Coltrain, Gage L.
2013-01-01
A major goal in the field of ionic liquids is correlating transport property trends with the underlying liquid structure of the compounds, such as the degree of charge organization among the constituent ions. Traditional techniques for experimentally assessing charge organization are specialized and not readily available for routine measurements. This represents a significant roadblock in elucidating these correlations. We use a combination of transmission and polarized-ATR infrared spectroscopy to measure the degree of charge organization for ionic liquids. The technique is illustrated with a family of 1-alkyl-3-methylimidazolium trifluoromethansulfonate ionic liquids at 30°C. As expected, the amount of charge organization decreases as the alkyl side chain is lengthened, highlighting the important role of short-range repulsive interactions in defining quasilattice structure. Inherent limitations of the method are identified and discussed. The quantitative measurements of charge organization are then correlated with trends in the transport properties of the compounds to highlight the relationship between charge and momentum transport and the underlying liquid structure. Most research laboratories possess infrared spectrometers capable of conducting these measurements, thus, the proposed method may represent a cost-effective solution for routinely measuring charge organization in ionic liquids. PMID:23781877
NASA Astrophysics Data System (ADS)
Chaurasia, S. K.; Saroj, A. L.; Shalu, Singh, V. K.; Tripathi, A. K.; Gupta, A. K.; Verma, Y. L.; Singh, R. K.
2015-07-01
Preparation and characterization of polymer electrolyte films of PEO+10wt.% LiPF6 + xwt.% BMIMPF6 (1-butyl-3-methylimidazolium hexafluorophosphate) containing dopant salt lithium hexafluorophosphate (LiPF6) and ionic liquid (BMIMPF6) having common anion PF6 - are reported. The ionic conductivity of the polymer electrolyte films has been found to increase with increasing concentration of BMIMPF6 in PEO+10 wt.% LiPF6 due to the plasticization effect of ionic liquid. DSC and XRD results show that the crystallinity of polymer electrolyte decreases with BMIMPF6 concentration which, in turn, is responsible for the increase in ionic conductivity. FTIR spectroscopic study shows the complexation of salt and/or ionic liquid cations with the polymer backbone. Ion dynamics behavior of PEO+LiPF6 as well as PEO+LiPF6 + BMIMPF6 polymer electrolytes was studied by frequency dependent conductivity, σ(f) measurements. The values σ(f) at various temperatures have been analyzed in terms of Jonscher power law (JPL) and scaled with respect to frequency which shows universal power law characteristics at all temperatures.
Performance of carbon-carbon supercapacitors based on organic, aqueous and ionic liquid electrolytes
NASA Astrophysics Data System (ADS)
Lewandowski, Andrzej; Olejniczak, Angelika; Galinski, Maciej; Stepniak, Izabela
Properties of capacitors working with the same carbon electrodes (activated carbon cloth) and three types of electrolytes: aqueous, organic and ionic liquids were compared. Capacitors filled with ionic liquids worked at a potential difference of 3.5 V, their solutions in AN and PC were charged up to the potential difference of 3 V, classical organic systems to 2.5 V and aqueous to 1 V. Cyclic voltammetry, galvanostatic charging/discharging and impedance spectroscopy were used to characterize these capacitors. The highest specific energy was recorded for the device working with ionic liquids, while the highest power is characteristic for the device filled with aqueous H 2SO 4 electrolyte. Aqueous electrolytes led to energy density an order of magnitude lower in comparison to that characteristic of ionic liquids.
NASA Technical Reports Server (NTRS)
Morales, Wilfredo; Koch, Victor R.; Street, Kenneth W., Jr.; Richard, Ryan M.
2008-01-01
Ionic liquids are salts, many of which are typically viscous fluids at room temperature. The fluids are characterized by negligible vapor pressures under ambient conditions. These properties have led us to study the effectiveness of ionic liquids containing both organic cations and anions for use as space lubricants. In the previous paper we have measured the vapor pressure and some tribological properties of two distinct ionic liquids under simulated space conditions. In this paper we will present vapor pressure measurements for two new ionic liquids and friction coefficient data for boundary lubrication conditions in a spiral orbit tribometer using stainless steel tribocouples. In addition we present the first tribological data on mixed ionic liquids and an ionic liquid additive. Post mortem infrared and Raman analysis of the balls and races indicates the major degradation pathway for these two organic ionic liquids is similar to those of other carbon based lubricants, i.e. deterioration of the organic structure into amorphous graphitic carbon. The coefficients of friction and lifetimes of these lubricants are comparable to or exceed these properties for several commonly used space oils.
Mixed organic compound-ionic liquid electrolytes for lithium battery electrolyte systems
NASA Astrophysics Data System (ADS)
Montanino, M.; Moreno, M.; Carewska, M.; Maresca, G.; Simonetti, E.; Lo Presti, R.; Alessandrini, F.; Appetecchi, G. B.
2014-12-01
The thermal, transport, rheological and flammability properties of electrolyte mixtures, proposed for safer lithium-ion battery systems, were investigated as a function of the mole composition. The blends were composed of a lithium salt (LiTFSI), organic solvents (namely EC, DEC) and an ionic liquid (PYR13TFSI). The main goal is to combine the fast ion transport properties of the organic compounds with the safe issues of the non-flammable and non-volatile ionic liquids. Preliminary tests in batteries have evidenced cycling performance approaching that observed in commercial organic electrolytes.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kellar, Michael
2015-09-01
The final portion of this project was accomplished at Sandia National Labs, Livermore, with the overall goal being to optimize lithium-air cells with an ionic liquid electrolyte. Both of these are potential future routes for lithium-ion technology. Lithiumair presents the advantage of higher gravimetric energy density, and ionic liquids present the advantage of greater hydrophobicity and much lower volatility, along with a larger window of electrochemical stability. Ionic liquids however have several drawbacks for the battery industry. Currently they are not as cost effective as many organic solvents. Additionally, because of the added viscosity of ionic interactions compared to themore » typical dipole interactions of a solvent, the ionic conductivity is lower than for common organic solvents.« less
Novel polymeric LIT and divalent cation fast ion conducting materials
NASA Astrophysics Data System (ADS)
Angell, C. A.
Solid state energy devices require a component which conducts electricity by ionic migration. The conductivity of this element of the system must be very high. Four types of materials show the promise to provide the necessary conductivity characteristics, while offering other desirable features such as the ability to distort in shape under mechanical stresses: (1) crystalline; (2) plastic crystal; (3) inorganic glassy; and (4) polymer salt solutions. This document reports on the following materials: lead halide-containing fast ion conducting glasses (LiF-PbF2-Al(PO3)3), mixed ionic electronic conduction (Na2O-V2O5-TeO2), alpha relaxation in ionic glasses, glass transition in P2O2, and conductivity transition between all-halide and all-oxide glasses.
Shahvelayati, Ashraf S; Ghazvini, Maryam; Yadollahzadeh, Khadijeh; Delbari, Akram S
2018-01-01
The development of multicomponent reactions (MCRs) in the presence of task-specific ionic liquids (ILs), used not only as environmentally benign reaction media, but also as catalysts, is a new approach that meet with the requirements of sustainable chemistry. In recent years, the use of ionic liquids as a green media for organic synthesis has become a chief study area. This is due to their unique properties such as non-volatility, non-flammability, chemical and thermal stability, immiscibility with both organic compounds and water and recyclability. Ionic liquids are used as environmentally friendly solvents instead of hazardous organic solvents. We report the condensation reaction between α-oximinoketone and dialkyl acetylene dicarboxylate in the presence of triphenylphosphine to afford substituted pyrroles under ionic liquid conditions in good yields. Densely functionalized pyrroles was easily prepared from reaction of α-oximinoketones, dialkyl acetylene dicarboxylate in the presence of triphenylphosphine in a quantitative yield under ionic liquid conditions at room temperature. In conclusion, ionic liquids are indicated as a useful and novel reaction medium for the selective synthesis of functionalized pyrroles. This reaction medium can replace the use of hazardous organic solvents. Easy work-up, synthesis of polyfunctional compounds, decreased reaction time, having easily available-recyclable ionic liquids, and good to high yields are advantages of present method. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.
[Pigment and ion transport in the vestibular organ].
Meyer zum Gottesberge-Orsulakova, A
1985-07-01
Pigments are found in various parts of the inner ear, especially in the neighbourhood of epithelia, which are supposed to be involved in the secretion and/or absorbtion of the endolymphatic fluid. Microprobe analysis (laser absorption mass micro analyzer "LAMMA" and X-ray) combined with morphological observations were performed in shock frozen, freeze-dried and plastic embedded inner ear tissue from the vestibular organ of pigmented guinea pig. Disturbance of the endolymphatic ionic composition (increased Na+) due to treatment with metabolic inhibitors (ethacrynic acid, ouabain) stimulated the migration of pigment granules and displacement of the dentritic processes of the melanocytes in a close vicinity to the presumably transporting vestibular epithelia (the dark and light cells and capillaries). The melanosomes obtained full range of metal ions that changed characteristically after treatment with metabolic inhibitors. It could be supposed that melanin presents some kind of reservoir for essential trace elements or compounds and may regulate numerous enzymatic and membrane functions by binding and releasing the metal ions.
NASA Astrophysics Data System (ADS)
Garbovskiy, Y.; Klimusheva, G.; Mirnaya, T.
2016-09-01
Mesomorphic metal alkanoates is very promising yet overlooked class of nonlinear-optical materials. Metal alkanoates can exhibit a broad variety of condensed states of matter including solid crystals, plastic crystals, lyotropic and thermotropic ionic liquid crystals, liquids, mesomorphic glasses, and Langmuir-Blodgett films. Glass-forming properties of metal alkanoates combined with their use as nano-reactors and anisotropic host open up simple and efficient way to design various photonic nanomaterials. Despite very interesting physics, the experimental data on optical and nonlinearoptical properties of such materials are scarce. The goal of the present paper is to fill the gap by discussing recent advances in the field of photonic materials made of metal alkanoates, organic dyes, and nanoparticles. Optical and nonlinear-optical properties of the following materials are reviewed: (i) mesomorphic glass doped with organic dyes; (ii) smectic glass composed of cobalt alkanoates; (iii) semiconductor nanoparticles embedded in a glassy host; (iv) metal nanoparticles - glass (the cobalt octanoate) nanocomposites.
Yasin, Siti Mariah Mohd; Ibrahim, Suriani; Johan, Mohd Rafie
2014-01-01
New solid polymer electrolytes (SPE) based on poly(ethylene oxide) (PEO) doped with lithium trifluoromethanesulfonate (LiCF3SO3), dibutyl phthalate (DBP) plasticizer, and zirconium oxide (ZrO2) nanoparticles were prepared by solution-casting technique. The conductivity was enhanced by addition of dibutyl phthalate (DBP) plasticizer and ZrO2 nanofiller with maximum conductivity (1.38 × 10(-4) Scm(-1)). The absorption edge and band gap values showed decreases upon addition of LiSO3CF3, DBP, and ZrO2 due to the formation of localized states in the SPE and the degree of disorder in the films increased.
Yasin, Siti Mariah Mohd; Ibrahim, Suriani
2014-01-01
New solid polymer electrolytes (SPE) based on poly(ethylene oxide) (PEO) doped with lithium trifluoromethanesulfonate (LiCF3SO3), dibutyl phthalate (DBP) plasticizer, and zirconium oxide (ZrO2) nanoparticles were prepared by solution-casting technique. The conductivity was enhanced by addition of dibutyl phthalate (DBP) plasticizer and ZrO2 nanofiller with maximum conductivity (1.38 × 10−4 Scm−1). The absorption edge and band gap values showed decreases upon addition of LiSO3CF3, DBP, and ZrO2 due to the formation of localized states in the SPE and the degree of disorder in the films increased. PMID:25133244
ERIC Educational Resources Information Center
Verdía, Pedro; Santamarta, Francisco; Tojo, Emilia
2017-01-01
An experiment for an undergraduate organic chemistry class based on the application of an ionic liquid as solvent and catalyst of an organic reaction is reported. The whole experiment requires three 3-h lab sessions. First, students prepare the ionic liquid dimethylimidazolium methylsulfate, which is then used as a recyclable catalyst/reaction…
Thermotropic Ionic Liquid Crystals
Axenov, Kirill V.; Laschat, Sabine
2011-01-01
The last five years’ achievements in the synthesis and investigation of thermotropic ionic liquid crystals are reviewed. The present review describes the mesomorphic properties displayed by organic, as well as metal-containing ionic mesogens. In addition, a short overview on the ionic polymer and self-assembled liquid crystals is given. Potential and actual applications of ionic mesogens are also discussed. PMID:28879986
Thermotropic Ionic Liquid Crystals.
Axenov, Kirill V; Laschat, Sabine
2011-01-14
The last five years' achievements in the synthesis and investigation of thermotropic ionic liquid crystals are reviewed. The present review describes the mesomorphic properties displayed by organic, as well as metal-containing ionic mesogens. In addition, a short overview on the ionic polymer and self-assembled liquid crystals is given. Potential and actual applications of ionic mesogens are also discussed.
Zhao, Y X; Shon, H K; Phuntsho, S; Gao, B Y
2014-02-15
This study is the first attempt to investigate the effect of total hardness and ionic strength on coagulation performance and the floc characteristics of titanium tetrachloride (TiCl4). Membrane fouling under different total hardness and ionic strength conditions was also evaluated during a coagulation-ultrafiltration (C-UF) hybrid process. Coagulation experiments were performed with two simulated waters, using humic acid (HA, high molecular weight) and fulvic acid (FA, relatively low molecular weight), respectively, as model natural organic matter (NOM). Results show that both particle and organic matter removal can be enhanced by increasing total hardness and ionic strength. Floc characteristics were significantly influenced by total hardness and ionic strength and were improved in terms of floc size, growth rate, strength, recoverability and compactness. The results of the UF tests show that the pre-coagulation with TiCl4 significantly improves the membrane permeate fluxes. Under different total hardness and ionic strength conditions, the membrane permeate flux varied according to both NOM and floc characteristics. The increase in total hardness and ionic strength improved the membrane permeate flux in the case of HA simulated water treatment. Copyright © 2014 Elsevier Ltd. All rights reserved.
Biodegradable films from isolate of sunflower (Helianthus annuus) proteins.
Ayhllon-Meixueiro, F; Vaca-Garcia, C; Silvestre, F
2000-07-01
The film-forming potential of isolate of sunflower proteins (ISFP) was investigated. Homogeneous films were obtained by dissolution of ISFP in alkaline water (pH 12), addition of a plasticizer, casting, and drying. Maximum protein solubilization and unfolding led to films with the highest elasticity. The effects of five dissolving bases and five plasticizers on the mechanical properties were studied. The use of ionic bases (LiOH, NaOH) capable of interfering with the interproteic noncovalent bonds resulted in the greatest tensile strength (sigma(max)) and elongation at break (epsilon(max)) values (3.9 MPa and 215-251%, respectively). Plasticizers conferred diverse tensile properties to the films: the use of 1,3-propanediol resulted in the highest sigma(max) (27.1 MPa), and glycerol resulted in the greatest epsilon(max) (251%). Different mechanical properties were obtained by using mixtures of these plasticizers.
Ionic Liquid Crystals: Versatile Materials.
Goossens, Karel; Lava, Kathleen; Bielawski, Christopher W; Binnemans, Koen
2016-04-27
This Review covers the recent developments (2005-2015) in the design, synthesis, characterization, and application of thermotropic ionic liquid crystals. It was designed to give a comprehensive overview of the "state-of-the-art" in the field. The discussion is focused on low molar mass and dendrimeric thermotropic ionic mesogens, as well as selected metal-containing compounds (metallomesogens), but some references to polymeric and/or lyotropic ionic liquid crystals and particularly to ionic liquids will also be provided. Although zwitterionic and mesoionic mesogens are also treated to some extent, emphasis will be directed toward liquid-crystalline materials consisting of organic cations and organic/inorganic anions that are not covalently bound but interact via electrostatic and other noncovalent interactions.
Extraction of organic compounds with room temperature ionic liquids.
Poole, Colin F; Poole, Salwa K
2010-04-16
Room temperature ionic liquids are novel solvents with a rather specific blend of physical and solution properties that makes them of interest for applications in separation science. They are good solvents for a wide range of compounds in which they behave as polar solvents. Their physical properties of note that distinguish them from conventional organic solvents are a negligible vapor pressure, high thermal stability, and relatively high viscosity. They can form biphasic systems with water or low polarity organic solvents and gases suitable for use in liquid-liquid and gas-liquid partition systems. An analysis of partition coefficients for varied compounds in these systems allows characterization of solvent selectivity using the solvation parameter model, which together with spectroscopic studies of solvent effects on probe substances, results in a detailed picture of solvent behavior. These studies indicate that the solution properties of ionic liquids are similar to those of polar organic solvents. Practical applications of ionic liquids in sample preparation include extractive distillation, aqueous biphasic systems, liquid-liquid extraction, liquid-phase microextraction, supported liquid membrane extraction, matrix solvents for headspace analysis, and micellar extraction. The specific advantages and limitations of ionic liquids in these studies is discussed with a view to defining future uses and the need not to neglect the identification of new room temperature ionic liquids with physical and solution properties tailored to the needs of specific sample preparation techniques. The defining feature of the special nature of ionic liquids is not their solution or physical properties viewed separately but their unique combinations when taken together compared with traditional organic solvents. Copyright 2009 Elsevier B.V. All rights reserved.
Ionic Liquid-Liquid Chromatography: A New General Purpose Separation Methodology.
Brown, Leslie; Earle, Martyn J; Gîlea, Manuela A; Plechkova, Natalia V; Seddon, Kenneth R
2017-08-10
Ionic liquids can form biphasic solvent systems with many organic solvents and water, and these solvent systems can be used in liquid-liquid separations and countercurrent chromatography. The wide range of ionic liquids that can by synthesised, with specifically tailored properties, represents a new philosophy for the separation of organic, inorganic and bio-based materials. A customised countercurrent chromatograph has been designed and constructed specifically to allow the more viscous character of ionic liquid-based solvent systems to be used in a wide variety of separations (including transition metal salts, arenes, alkenes, alkanes, bio-oils and sugars).
Ionic Transport Through Metal-Rich Organic Coatings
2016-08-19
COVERED October 2013-Septermber 2015 4. TITLE AND SUBTITLE Ionic Transport Through Metal-Rich Organic Coatings 5a. CONTRACT NUMBER 5b. GRANT...NOTES 14. ABSTRACT Organic coatings are commonly used on aircraft and in the automotive industry to protect against corrosive environments. Although...volume (MPV) percent, solvent polarity, and resin molecular weight impact corrosion protection of metal-rich organic (MRO) coatings. Following design
Ionic Transport Through Metal-Rich Organic Coatings
2016-08-19
COVERED October 2013-Septermber 2015 4. TITLE AND SUBTITLE Ionic Transport Through Metal-Rich Organic Coatings 5a. CONTRACT NUMBER 5b. GRANT...14. ABSTRACT Organic coatings are commonly used on aircraft and in the automotive industry to protect against corrosive environments. Although...volume (MPV) percent, solvent polarity, and resin molecular weight impact corrosion protection of metal-rich organic (MRO) coatings. Following design of
DOE Office of Scientific and Technical Information (OSTI.GOV)
Hegde, Govind A.; Bharadwaj, Vivek S.; Kinsinger, Corey L.
2016-08-14
The recalcitrance of lignocellulosic biomass poses a major challenge that hinders the economical utilization of biomass for the production of biofuel, plastics, and chemicals. Ionic liquids have become a promising solvent that addresses many issues in both the pretreatment process and the hydrolysis of the glycosidic bond for the deconstruction of cellulosic materials. However, to make the use of ionic liquids economically viable, either the cost of ionic liquids must be reduced, or a less expensive solvent (e.g., water) may be added to reduce the overall amount of ionic liquid used in addition to reducing the viscosity of the binarymore » liquid mixture. In this work, we employ atomistic molecular dynamics simulations to investigate the impact of water dilution on the overall liquid structure and properties of three imidazolium based ionic liquids. It is found that ionic liquid-water mixtures exhibit characteristics that can be grouped into two distinct regions, which are a function of the ionic liquid concentration. The trends observed in each region are found to correlate with the ordering in the local structure of the ionic liquid that arises from the dynamic interactions between the ion pairs. Simulation results suggest that there is a high level of local ordering in the molecular structure at high concentrations of ionic liquids that is driven by the aggregation of the cationic tails and the anion-water interactions. It is found that as the concentration of ionic liquids in the binary mixture is decreased, there is a point at which the competing self and cross interaction energies between the ionic liquid and water shifts away from a cation-anion dominated regime, which results in a significant change in the mixture properties. This break point, which occurs around 75% w/w ionic liquids, corresponds to the point at which water molecules percolate into the ionic liquid network disrupting the ionic liquids’ nanostructure. It is observed that as the cationic alkyl tail length increases, the changes in the binary mixtures’ properties become more pronounced.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Koech, Phillip K.; Malhotra, Deepika; Heldebrant, David J.
2015-01-01
Climate change is partly attributed to global anthropogenic carbon dioxide (CO2) emission to the atmosphere. These environmental effects can be mitigated by CO2 capture, utilization and storage. Alkanolamine solvents, such as monoethanolamine (MEA), which bind CO2 as carbamates or bicarbonate salts are used for CO2 capture in niche applications. These solvents consist of approximately 30 wt% of MEA in water, exhibiting a low, CO2-rich viscosity, fast kinetics and favorable thermodynamics. However, these solvents have low CO2 capacity and high heat capacity of water, resulting in prohibitively high costs of thermal solvent regeneration. Effective capture of the enormous amounts of CO2more » produced by coal-fired plants requires a material with high CO2 capacity and low regeneration energy requirements. To this end, several water-lean transformational solvents systems have been developed in order to reduce these energy penalties. These technologies include nano-material organic hybrids (NOHMs), task-specific, protic and conventional ionic liquids, phase change solvents. As part of an ongoing program in our group, we have developed new water lean transformational solvents known as CO2 binding organic liquids (CO2BOLs) which have the potential to be energy efficient CO2 capture solvents. These solvents, also known as switchable ionic liquids meaning, are organic solvents that can reversibly transform from non- ionic to ionic form and back. The zwitterionic state in these liquids is formed when low polarity non-ionic alkanolguanidines or alkanolamidines react with CO2 or SO2 to form ionic liquids with high polarity. These polar ionic liquids can be thermally converted to the less polar non-ionic solvent by releasing CO2.« less
Ionic-liquid materials for the electrochemical challenges of the future.
Armand, Michel; Endres, Frank; MacFarlane, Douglas R; Ohno, Hiroyuki; Scrosati, Bruno
2009-08-01
Ionic liquids are room-temperature molten salts, composed mostly of organic ions that may undergo almost unlimited structural variations. This review covers the newest aspects of ionic liquids in applications where their ion conductivity is exploited; as electrochemical solvents for metal/semiconductor electrodeposition, and as batteries and fuel cells where conventional media, organic solvents (in batteries) or water (in polymer-electrolyte-membrane fuel cells), fail. Biology and biomimetic processes in ionic liquids are also discussed. In these decidedly different materials, some enzymes show activity that is not exhibited in more traditional systems, creating huge potential for bioinspired catalysis and biofuel cells. Our goal in this review is to survey the recent key developments and issues within ionic-liquid research in these areas. As well as informing materials scientists, we hope to generate interest in the wider community and encourage others to make use of ionic liquids in tackling scientific challenges.
Ionic-liquid materials for the electrochemical challenges of the future
NASA Astrophysics Data System (ADS)
Armand, Michel; Endres, Frank; Macfarlane, Douglas R.; Ohno, Hiroyuki; Scrosati, Bruno
2009-08-01
Ionic liquids are room-temperature molten salts, composed mostly of organic ions that may undergo almost unlimited structural variations. This review covers the newest aspects of ionic liquids in applications where their ion conductivity is exploited; as electrochemical solvents for metal/semiconductor electrodeposition, and as batteries and fuel cells where conventional media, organic solvents (in batteries) or water (in polymer-electrolyte-membrane fuel cells), fail. Biology and biomimetic processes in ionic liquids are also discussed. In these decidedly different materials, some enzymes show activity that is not exhibited in more traditional systems, creating huge potential for bioinspired catalysis and biofuel cells. Our goal in this review is to survey the recent key developments and issues within ionic-liquid research in these areas. As well as informing materials scientists, we hope to generate interest in the wider community and encourage others to make use of ionic liquids in tackling scientific challenges.
Burt, Ryan; Breitsprecher, Konrad; Daffos, Barbara; Taberna, Pierre-Louis; Simon, Patrice; Birkett, Greg; Zhao, X S; Holm, Christian; Salanne, Mathieu
2016-10-06
Nanoporous carbon-based supercapacitors store electricity through adsorption of ions from the electrolyte at the surface of the electrodes. Room temperature ionic liquids, which show the largest ion concentrations among organic liquid electrolytes, should in principle yield larger capacitances. Here, we show by using electrochemical measurements that the capacitance is not significantly affected when switching from a pure ionic liquid to a conventional organic electrolyte using the same ionic species. By performing additional molecular dynamics simulations, we interpret this result as an increasing difficulty of separating ions of opposite charges when they are more concentrated, that is, in the absence of a solvent that screens the Coulombic interactions. The charging mechanism consistently changes with ion concentration, switching from counterion adsorption in the diluted organic electrolyte to ion exchange in the pure ionic liquid. Contrarily to the capacitance, in-pore diffusion coefficients largely depend on the composition, with a noticeable slowing of the dynamics in the pure ionic liquid.
NASA Astrophysics Data System (ADS)
Takeya, J.
2008-10-01
The environment of surface electrons at 'solid-to-liquid' interfaces is somewhat extreme, subjected to intense local electric fields or harsh chemical pressures that high-density ionic charge or polarization of mobile molecules create. In this proceedings, we argue functions of electronic carriers generated at the surface of organic semiconductor crystals in response to the local electric fields in the very vicinity of the interface to ionic liquid. The ionic liquids (ILs), or room temperature molten salts, are gaining considerable interest in the recent decade at the prospect of nonvolatile 'green solvents', with the development of chemically stable and nontoxic compounds. Moreover, such materials are also applied to electrolytes for lithium ion batteries and electric double-layer (EDL) capacitors. Our present solid-to-liquid interfaces of rubrene single crystals and ionic liquids work as fast-switching organic field-effect transistors (OFETs) with the highest transconductance, i.e. the most efficient response of the output current to the input voltage, among the OFETs ever built.
Highly Conductive, Stretchable, and Transparent Solid Polymer Electrolyte Membrane
NASA Astrophysics Data System (ADS)
He, Ruixuan; Echeverri, Mauricio; Kyu, Thein
2014-03-01
With the guidance of ternary phase diagrams, completely amorphous polymer electrolyte membranes (PEM) were successfully prepared by melt processing for lithium-ion battery. The PEM under consideration consisted of poly (ethylene glycol diacrylate) (PEGDA), succinonitrile (SCN) and Lithium bis(trifluoro-methane)sulfonamide (LiTFSI). After UV-crosslinking, the PEM is transparent and light-weight. Addition of SCN plastic crystal affords not only dissociation of the lithium salt, but also plasticization to the crosslinked PEGDA network. Of particular importance is the achievement of room-temperature ionic conductivity of ~10-3 S/cm, which is comparable to that of commercial liquid electrolyte. Higher ionic conductivities were achieved at elevated temperatures or with use of a moderately higher molecular weight of PEGDA. In terms of electrochemical and chemical stability, the PEM exhibited oxidative stability up to 5 V against lithium reference electrode. Stable interface behavior between the PEM and lithium electrode is also seen with ageing time. In the tensile tests, samples containing low molecular weight PEGDA are stiffer, whereas the high molecular weight PEGDA is stretchable up to 80% elongation. Supported by NSF-DMR 1161070.
Creating Lithium-Ion Electrolytes with Biomimetic Ionic Channels in Metal-Organic Frameworks.
Shen, Li; Wu, Hao Bin; Liu, Fang; Brosmer, Jonathan L; Shen, Gurong; Wang, Xiaofeng; Zink, Jeffrey I; Xiao, Qiangfeng; Cai, Mei; Wang, Ge; Lu, Yunfeng; Dunn, Bruce
2018-06-01
Solid-state electrolytes are the key to the development of lithium-based batteries with dramatically improved energy density and safety. Inspired by ionic channels in biological systems, a novel class of pseudo solid-state electrolytes with biomimetic ionic channels is reported herein. This is achieved by complexing the anions of an electrolyte to the open metal sites of metal-organic frameworks (MOFs), which transforms the MOF scaffolds into ionic-channel analogs with lithium-ion conduction and low activation energy. This work suggests the emergence of a new class of pseudo solid-state lithium-ion conducting electrolytes. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Evolution of Osmolyte Systems.
ERIC Educational Resources Information Center
Banfalvi, Gaspar
1991-01-01
Osmotic aspects of aqueous solutions that are usually disregarded in biochemistry textbooks are presented. This article discusses the osmolarity of seawater, evolution of organisms over geological time, ionic adaptation of cells, ionic concentrations in bacteria, osmolytes and blood electrolytes in water-stressed organisms and land vertebrates,…
Heo, Jae Sang; Choi, Seungbeom; Jo, Jeong-Wan; Kang, Jingu; Park, Ho-Hyun; Kim, Yong-Hoon; Park, Sung Kyu
2017-01-01
In this paper, we demonstrate high mobility solution-processed metal-oxide thin-film transistors (TFTs) by using a high-frequency-stable ionic-type hybrid gate dielectric (HGD). The HGD gate dielectric, a blend of sol-gel aluminum oxide (AlOx) and poly(4-vinylphenol) (PVP), exhibited high dielectric constant (ε~8.15) and high-frequency-stable characteristics (1 MHz). Using the ionic-type HGD as a gate dielectric layer, an minimal electron-double-layer (EDL) can be formed at the gate dielectric/InOx interface, enhancing the field-effect mobility of the TFTs. Particularly, using the ionic-type HGD gate dielectrics annealed at 350 °C, InOx TFTs having an average field-effect mobility of 16.1 cm2/Vs were achieved (maximum mobility of 24 cm2/Vs). Furthermore, the ionic-type HGD gate dielectrics can be processed at a low temperature of 150 °C, which may enable their applications in low-thermal-budget plastic and elastomeric substrates. In addition, we systematically studied the operational stability of the InOx TFTs using the HGD gate dielectric, and it was observed that the HGD gate dielectric effectively suppressed the negative threshold voltage shift during the negative-illumination-bias stress possibly owing to the recombination of hole carriers injected in the gate dielectric with the negatively charged ionic species in the HGD gate dielectric. PMID:28772972
Liu, Ping; Guo, Xin; Nan, Fuchun; Duan, Yongxin; Zhang, Jianming
2017-01-25
Iridescent films formed from the self-assembly of cellulose nanocrystals (CNCs) are brittle and difficult to handle or integrate within an industrial process. Here we present a simple approach to prepare iridescent CNC films with tunable pliability and coloration through the addition of ionic liquids (ILs) of 1-allyl-3-methylimidazolium chloride (AmimCl) as plasticizers. By using the undried CNC film as a filter membrane and ILs solution as a leaching liquid, it was found that the filtration process made ILs uniformly interpenetrate into CNC film due to the strong ionic interaction between CNC and AmimCl. Unexpectedly, the filtration process also gave rise to partial desulfurization of CNC film, which is conducive to the improvement of thermal stability. Benefiting from the improved thermal stability and the dissolving capacity of AmimCl for cellulose at high temperature, the incorporated ILs enable the cholesteric CNC film to be further toughened via a hot-pressing treatment. This study demonstrates that ionic liquids have great potential to modify the mechanical, optical properties as well as the thermal stability of iridescent CNC films.
Recovery of sugars from ionic liquid biomass liquor by solvent extraction
Brennan, Timothy Charles R.; Holmes, Bradley M.; Simmons, Blake A.; Blanch, Harvey W.
2015-10-13
The present invention provides for a composition comprising a solution comprising (a) an ionic liquid (IL) or ionic liquid-aqueous (ILA) phase and (b) an organic phase, wherein the solution comprises a sugar and a boronic acid. The present invention also provides for a method of removing a sugar from a solution, comprising: (a) providing a solution comprising (i) an IL or ILA phase and (ii) an organic phase, wherein the solution comprises an IL, a sugar and a boronic acid; (b) contacting the sugar with the boronic acid to form a sugar-boronic acid complex, (c) separating the organic phase and the aqueous phase, wherein the organic phase contains the sugar-boronic acid complex, and optionally (d) separating the sugar from the organic phase.
Occurrence and effects of plastic additives on marine environments and organisms: A review.
Hermabessiere, Ludovic; Dehaut, Alexandre; Paul-Pont, Ika; Lacroix, Camille; Jezequel, Ronan; Soudant, Philippe; Duflos, Guillaume
2017-09-01
Plastics debris, especially microplastics, have been found worldwide in all marine compartments. Much research has been carried out on adsorbed pollutants on plastic pieces and hydrophobic organic compounds (HOC) associated with microplastics. However, only a few studies have focused on plastic additives. These chemicals are incorporated into plastics from which they can leach out as most of them are not chemically bound. As a consequence of plastic accumulation and fragmentation in oceans, plastic additives could represent an increasing ecotoxicological risk for marine organisms. The present work reviewed the main class of plastic additives identified in the literature, their occurrence in the marine environment, as well as their effects on and transfers to marine organisms. This work identified polybrominated diphenyl ethers (PBDE), phthalates, nonylphenols (NP), bisphenol A (BPA) and antioxidants as the most common plastic additives found in marine environments. Moreover, transfer of these plastic additives to marine organisms has been demonstrated both in laboratory and field studies. Upcoming research focusing on the toxicity of microplastics should include these plastic additives as potential hazards for marine organisms, and a greater focus on the transport and fate of plastic additives is now required considering that these chemicals may easily leach out from plastics. Copyright © 2017 Elsevier Ltd. All rights reserved.
Shen, Jian; Zhao, He; Cao, Hongbin; Zhang, Yi; Chen, Yongsheng
2014-02-01
Whether a cationic organic polymer can remove more total cyanide (TCN) than a non-ionic organic polymer during the same flocculation system has not been reported previously. In this study, the effects of organic polymers with different charge density on the removal mechanisms of TCN in coking wastewater are investigated by polyferric sulfate (PFS) with a cationic organic polymer (PFS-C) or a non-ionic polymer (PFS-N). The coagulation experiments results show that residual concentrations of TCN (Fe(CN)6(3-)) after PFS-C flocculation (TCN < 0.2 mg/L) are much lower than that after PFS-N precipitation. This can be attributed to the different TCN removal mechanisms of the individual organic polymers. To investigate the roles of organic polymers, physical and structural characteristics of the flocs are analyzed by FT-IR, XPS, TEM and XRD. Owing to the presence of N+ in PFS-C, Fe(CN)6(3-) and negative flocs (Fe(CN)6(3-) adsorbed on ferric hydroxides) can be removed via charge neutralization and electrostatic patch flocculation by the cationic organic polymer. However, non-ionic N in PFS-N barely reacts with cyanides through sweeping or bridging, which indicates that the non-ionic polymer has little influence on TCN removal.
Vaid, Thomas P; Kelley, Steven P; Rogers, Robin D
2017-07-01
Traditional synthesis of metal-organic frameworks (MOFs) involves the reaction of a metal-containing precursor with an organic linker in an organic solvent at an elevated temperature, in what is termed a 'solvothermal' reaction. More recently, many examples have been reported of MOF synthesis in ionic liquids (ILs), rather than an organic solvent, in 'ionothermal' reactions. The high concentration of both cations and anions in an ionic liquid allows for the formation of new MOF structures in which the IL cation or anion or both are incorporated into the MOF. Most commonly, the IL cation is included in the open cavities of the MOF, countering the anionic charge of the MOF framework itself and acting as a template around which the MOF structure forms. Ionic liquids can also serve other structure-directing roles, for example, when an IL containing a single enantiomer of a chiral anion leads to a homochiral MOF, even though the IL anion is not itself incorporated into the MOF. A comprehensive review of ionothermal syntheses of MOFs, and the structure-directing effects of the ILs, is given.
Antibacterial activity and toxicity of silver - nanosilver versus ionic silver
NASA Astrophysics Data System (ADS)
Kvitek, L.; Panacek, A.; Prucek, R.; Soukupova, J.; Vanickova, M.; Kolar, M.; Zboril, R.
2011-07-01
The in vitro study of antibacterial activity of silver nanoparticles (NPs), prepared via modified Tollens process, revealed high antibacterial activity even at very low concentrations around several units of mg/L. These concentrations are comparable with concentrations of ionic silver revealing same antibacterial effect. However, such low concentrations of silver NPs did not show acute cytotoxicity to mammalian cells - this occurs at concentrations higher than 60 mg/L of silver, while the cytotoxic level of ionic silver is much more lower (approx. 1 mg/L). Moreover, the silver NPs exhibit lower acute ecotoxicity against the eukaryotic organisms such as Paramecium caudatum, Monoraphidium sp. and D. melanogaster. The silver NPs are toxic to these organisms at the concentrations higher than 30 mg/L of silver. On contrary, ionic silver retains its cytoxicity and ecotoxicity even at the concentration equal to 1 mg/L. The performed experiments demonstrate significantly lower toxicity of silver NPs against the eukaryotic organisms than against the prokaryotic organisms.
NASA Astrophysics Data System (ADS)
Pal, P.; Ghosh, A.
2017-07-01
We have studied the charge carrier dynamics in poly(methylmethacrylate)-LiClO4 polymer electrolytes plasticized with different plasticizers such as ethylene carbonate (EC), propylene carbonate (PC), polyethylene glycol (PEG), and dimethyl carbonate (DMC). We have measured the broadband complex conductivity spectra of these electrolytes in the frequency range of 0.01 Hz-3 GHz and in the temperature range of 203 K-363 K and analyzed the conductivity spectra in the framework of the random barrier model by taking into account the contribution of the electrode polarization observed at low frequencies and/or at high temperatures. It is observed that the temperature dependences of the ionic conductivity and relaxation time follow the Vogel-Tammann-Fulcher relation for all plasticized electrolytes. We have also performed the scaling of the conductivity spectra, which indicates that the charge carrier dynamics is almost independent of temperature and plasticizers in a limited frequency range. The existence of nearly constant loss in these electrolytes has been observed at low temperatures and/or high frequencies. We have studied the dielectric relaxation in these electrolytes using electric modulus formalism and obtained the stretched exponent and the decay function. We have observed less cooperative ion dynamics in electrolytes plasticized with DMC compared to electrolytes plasticized with EC, PC, and PEG.
Ionic thermoelectric gating organic transistors
Zhao, Dan; Fabiano, Simone; Berggren, Magnus; Crispin, Xavier
2017-01-01
Temperature is one of the most important environmental stimuli to record and amplify. While traditional thermoelectric materials are attractive for temperature/heat flow sensing applications, their sensitivity is limited by their low Seebeck coefficient (∼100 μV K−1). Here we take advantage of the large ionic thermoelectric Seebeck coefficient found in polymer electrolytes (∼10,000 μV K−1) to introduce the concept of ionic thermoelectric gating a low-voltage organic transistor. The temperature sensing amplification of such ionic thermoelectric-gated devices is thousands of times superior to that of a single thermoelectric leg in traditional thermopiles. This suggests that ionic thermoelectric sensors offer a way to go beyond the limitations of traditional thermopiles and pyroelectric detectors. These findings pave the way for new infrared-gated electronic circuits with potential applications in photonics, thermography and electronic-skins. PMID:28139738
Montalbán, Mercedes G; Collado-González, Mar; Lozano-Pérez, A Abel; Baños, F Guillermo Díaz; Víllora, Gloria
2018-08-01
This data article is related to the subject of the research article "Extraction of Organic Compounds Involved in the Kinetic Resolution of rac-2-Pentanol from n-Hexane by Imidazolium-based Ionic Liquids: Liquid-Liquid Equilibrium" (Montalbán et al., 2018) [1]. It contains experimental data of density and refractive index of binary and ternary mixtures of imidazolium-based ionic liquids, n -hexane and organic compounds involved in the kinetic resolution of rac -2-pentanol ( rac -2-pentanol, vinyl butyrate, rac -2-pentyl butyrate or butyric acid) measured at 303.15 K and 1 atm. These data are presented as calibration curves which help to determine the composition of the ionic liquid-rich phase knowing its density or refractive index.
Acidic precipitation at a site within the northeastern conurbation
Jay S. Jacobson; Laurence I. Heller; Paul Van Leuken
1976-01-01
Rain and snow were collected in plastic beakers either manually or with a Wong sampler during 58 precipitation events in 1974 at Yonkers, New York approximately 24 km north of the center of New York City. Determinations were made of total dissolved ionic species, free hydrogen ions, total hydrogen ions, sulfate, nitrate, chloride, and fluoride. Conductivity...
Ionic Liquids as Extraction Media for Metal Ions
NASA Astrophysics Data System (ADS)
Hirayama, Naoki
In solvent extraction separation of metal ions, recently, many researchers have investigated possible use of hydrophobic ionic liquids as extraction media instead of organic solvents. Ionic liquids are salts of liquid state around room temperature and can act not only as solvents but also as ion-exchangers. Therefore, the extraction mechanism of metal ions into ionic liquids is complicated. This review presents current overview and perspective on evaluation of nature of hydrophobic ionic liquids as extraction media for metal ions.
Molecular and ionic mimicry and the transport of toxic metals
Bridges, Christy C.; Zalups, Rudolfs K.
2008-01-01
Despite many scientific advances, human exposure to, and intoxication by, toxic metal species continues to occur. Surprisingly, little is understood about the mechanisms by which certain metals and metal-containing species gain entry into target cells. Since there do not appear to be transporters designed specifically for the entry of most toxic metal species into mammalian cells, it has been postulated that some of these metals gain entry into target cells, through the mechanisms of ionic and/or molecular mimicry, at the site of transporters of essential elements and/or molecules. The primary purpose of this review is to discuss the transport of selective toxic metals in target organs and provide evidence supporting a role of ionic and/or molecular mimicry. In the context of this review, molecular mimicry refers to the ability of a metal ion to bond to an endogenous organic molecule to form an organic metal species that acts as a functional or structural mimic of essential molecules at the sites of transporters of those molecules. Ionic mimicry refers to the ability of a cationic form of a toxic metal to mimic an essential element or cationic species of an element at the site of a transporter of that element. Molecular and ionic mimics can also be sub-classified as structural or functional mimics. This review will present the established and putative roles of molecular and ionic mimicry in the transport of mercury, cadmium, lead, arsenic, selenium, and selected oxyanions in target organs and tissues. PMID:15845419
Molecular and ionic mimicry and the transport of toxic metals
DOE Office of Scientific and Technical Information (OSTI.GOV)
Bridges, Christy C.; Zalups, Rudolfs K.
Despite many scientific advances, human exposure to, and intoxication by, toxic metal species continues to occur. Surprisingly, little is understood about the mechanisms by which certain metals and metal-containing species gain entry into target cells. Since there do not appear to be transporters designed specifically for the entry of most toxic metal species into mammalian cells, it has been postulated that some of these metals gain entry into target cells, through the mechanisms of ionic and/or molecular mimicry, at the site of transporters of essential elements and/or molecules. The primary purpose of this review is to discuss the transport ofmore » selective toxic metals in target organs and provide evidence supporting a role of ionic and/or molecular mimicry. In the context of this review, molecular mimicry refers to the ability of a metal ion to bond to an endogenous organic molecule to form an organic metal species that acts as a functional or structural mimic of essential molecules at the sites of transporters of those molecules. Ionic mimicry refers to the ability of a cationic form of a toxic metal to mimic an essential element or cationic species of an element at the site of a transporter of that element. Molecular and ionic mimics can also be sub-classified as structural or functional mimics. This review will present the established and putative roles of molecular and ionic mimicry in the transport of mercury, cadmium, lead, arsenic, selenium, and selected oxyanions in target organs and tissues.« less
Potentiometric and ion-selective electrode titrations together with batch sorption/desorption experiments, were performed to explain the aqueous and surface complexation reactions between kaolinite, Pb, Cd and three organic acids. Variables included pH, ionic strength, metal conc...
DETERMINATION OF HENRY'S LAW CONSTANTS FOR VOCS IN ROOM TEMPERATURE IONIC LIQUIDS
Ionic liquids (ILs) have been shown to be a newer medium for a wide variety of chemical reactions and are considered as the potential replacements for traditional volatile organic solvents. However, the separation and recovery of organic compounds from ILs has not been systematic...
Developmental emergence of different forms of neuromodulation in Aplysia sensory neurons.
Marcus, E A; Carew, T J
1998-04-14
The capacity for neuromodulation and biophysical plasticity is a defining feature of most mature neuronal cell types. In several cases, modulation at the level of the individual neuron has been causally linked to changes in the functional output of a neuronal circuit and subsequent adaptive changes in the organism's behavioral responses. Understanding how such capacity for neuromodulation develops therefore may provide insights into the mechanisms both of neuronal development and learning and memory. We have examined the development of multiple forms of neuromodulation triggered by a common neurotransmitter, serotonin, in the pleural sensory neurons of Aplysia californica. We have found that multiple signaling cascades within a single neuron develop sequentially, with some being expressed only very late in development. In addition, our data suggest a model in which, within a single neuromodulatory pathway, the elements of the signaling cascade are developmentally expressed in a "retrograde" manner with the ionic channel that is modulated appearing early in development, functional elements in the second messenger cascade appearing later, and finally, coupling of the second messenger cascade to the serotonin receptor appearing quite late. These studies provide the characterization of the development of neuromodulation at the level of an identified cell type and offer insights into the potential roles of neuromodulatory processes in development and adult plasticity.
Leaching characteristics of polybrominated diphenyl ethers (PBDEs) from flame-retardant plastics.
Kim, Yong-Jin; Osako, Masahiro; Sakai, Shin-ichi
2006-10-01
To investigate the effect of leachant on the leachability of polybrominated diphenyl ethers (PBDEs), we determined the leaching concentrations of PBDEs from flame-retardant plastic samples (TV housings and raw materials before molding processing) that are regarded as a source of PBDEs in landfill sites. The leachants used were distilled water, 20% methanol solution, and dissolved humic solution (DHS) of 1000 mg/l based on organic carbon. The leaching test conditions were a liquid-to-solid ratio of 100:1, and a contact period of five days, with twice-daily agitation in a temperature-controlled room of 30 degrees C without pH or ionic strength control. The leaching concentrations of PBDEs increased with increased content, and were found to be remarkably enhanced when methanol and DHS were used instead of distilled water. The enhancement of leachability in the presence of the latter was attributed to the cosolvency effect, and complex formations between the PBDEs and dissolved humic matter (DHM). PBDE concentrations in the leachate obtained from the leaching test and an actual landfill site revealed a significant presence of congeners below heptabromodiphenyl ethers (H7BDEs), detected in the leachate of the actual landfill, while significant amounts of nonabromodiphenyl ethers (N9BDEs) and decabromodiphenyl ether (D10BDE) were detected in the leachate of the leaching test.
Atmospheric Pressure Method and Apparatus for Removal of Organic Matter with Atomic and Ionic Oxygen
NASA Technical Reports Server (NTRS)
Banks, Bruce A. (Inventor); Rutledge, Sharon K. (Inventor)
1996-01-01
A gas stream containing ionic and atomic oxygen in inert gas is used to remove organic matter from a substrate. The gas stream is formed by flowing a mixture of gaseous oxygen in an inert gas such as helium at atmospheric pressure past a high voltage, current limited, direct current arc which contacts the gas mixture and forms the ionic and atomic oxygen. The arc is curved at the cathode end and the ionic oxygen formed by the arc nearer to the anode end of the arc is accelerated in a direction towards the cathode by virtue of its charge. The relatively high mass to charge ratio of the ionic oxygen enables at least some of it to escape the arc before contacting the cathode and it is directed onto the substrate. This is useful for cleaning delicate substrates such as fine and historically important paintings and delicate equipment and the like.
Atmospheric Pressure Method and Apparatus for Removal of Organic Matter with Atomic and Ionic Oxygen
NASA Technical Reports Server (NTRS)
Banks, Bruce A. (Inventor); Rutledge, Sharon K. (Inventor)
1997-01-01
A gas stream containing ionic and atomic oxygen in inert gas is used to remove organic matter from a substrate. The gas stream is formed by flowing a mixture of gaseous oxygen in an inert gas such as helium at atmospheric pressure past a high voltage, current limited, direct current arc which contacts the gas mixture and forms the ionic and atomic oxygen. The arc is curved at the cathode end and the ionic oxygen formed by the arc nearer to the anode end of the arc is accelerated in a direction towards the cathode by virtue of its charge. The relatively high mass to charge ratio of the ionic oxygen enables at least some of it to escape the arc before contacting the cathode and it is directed onto the substrate. This is useful for cleaning delicate substrates such as fine and historically important paintings and delicate equipment and the like.
Egorova, Ksenia S; Ananikov, Valentine P
2014-02-01
Rapid progress in the field of ionic liquids in recent decades led to the development of many outstanding energy-conversion processes, catalytic systems, synthetic procedures, and important practical applications. Task-specific optimization emerged as a sharpening stone for the fine-tuning of structure of ionic liquids, which resulted in unprecedented efficiency at the molecular level. Ionic-liquid systems showed promising opportunities in the development of green and sustainable technologies; however, the chemical nature of ionic liquids is not intrinsically green. Many ionic liquids were found to be toxic or even highly toxic towards cells and living organisms. In this Review, we show that biological activity and cytotoxicity of ionic liquids dramatically depend on the nature of a biological system. An ionic liquid may be not toxic for particular cells or organisms, but may demonstrate high toxicity towards another target present in the environment. Thus, a careful selection of biological activity data is a must for the correct assessment of chemical technologies involving ionic liquids. In addition to the direct biological activity (immediate response), several indirect effects and aftereffects are of primary importance. The following principal factors were revealed to modulate toxicity of ionic liquids: i) length of an alkyl chain in the cation; ii) degree of functionalization in the side chain of the cation; iii) anion nature; iv) cation nature; and v) mutual influence of anion and cation. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Martinis, Estefanía M; Olsina, Roberto A; Altamirano, Jorgelina C; Wuilloud, Rodolfo G
2009-05-15
A novel on-line preconcentration method based on liquid-liquid (L-L) extraction with room temperature ionic liquids (RTILs) coupled to flame atomic absorption spectrometry (FAAS) was developed for cadmium determination in plastic food packaging materials. The methodology is based on the complexation of Cd with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP) reagent after sample digestion followed by extraction of the complex with the RTIL 1-butyl-3-methylimidazolium hexafluorophosphate ([C(4)mim][PF(6)]). The mixture was loaded into a flow injection analysis (FIA) manifold and the RTIL rich-phase was retained in a microcolumn filled with silica gel. The RTIL rich-phase was then eluted directly into FAAS. A enhancement factor of 35 was achieved with 20 mL of sample. The limit of detection (LOD), obtained as IUPAC recommendation, was 6 ng g(-1) and the relative standard deviation (R.S.D.) for 10 replicates at 10 microg L(-1) Cd concentration level was 3.9%, calculated at the peak heights. The calibration graph was linear and a correlation coefficient of 0.9998 was achieved. The accuracy of the method was evaluated by both a recovery study and comparison of results with direct determination by electrothermal atomic absorption spectrometry (ETAAS). The method was successfully applied for Cd determination in plastic food packaging materials and Cd concentrations found were in the range of 0.04-10.4 microg g(-1).
von Goetz, Natalie; Fabricius, Lars; Glaus, Reto; Weitbrecht, Volker; Günther, Detlef; Hungerbühler, Konrad
2013-01-01
Food storage containers with embedded silver as an antibacterial agent promise longer durability of food. For risk assessment the release of this silver into the stored food and resulting human exposure need to be known. For the purpose of exposure assessment, silver migration from commercial plastic containers with declared content of 'nano-' or 'micro-silver' into different food simulants (water, 10% ethanol, 3% acetic acid, olive oil) was quantitatively determined by ICP-MS and the form of the released silver was investigated. The highest migration of silver was observed for the acidic food simulant with 30 ng silver cm(-2) contact surface within 10 days at 20°C. In a second and third use cycle, migration dropped by a factor of up to 10, so that the maximum cumulated release over three use cycles was 34 ng cm(-2). The silver release over time was described using a power function and a numerical model that simulates Fickian diffusion through the plastic material. The released silver was found to be in ionic form, but also in the form of silver nanoparticles (around 12%). Consumer exposure to the total amount of silver released from the food containers is low in comparison with the background silver exposure of the general population, but since natural background concentrations are only known for ionic silver, the exposure to silver nanoparticles is not directly comparable with a safe background level.
Plastic Muscles TM as lightweight, low voltage actuators and sensors
NASA Astrophysics Data System (ADS)
Bennett, Matthew; Leo, Donald; Duncan, Andrew
2008-03-01
Using proprietary technology, Discover Technologies has developed ionomeric polymer transducers that are capable of long-term operation in air. These "Plastic Muscle TM" transducers are useful as soft distributed actuators and sensors and have a wide range of applications in the aerospace, robotics, automotive, electronics, and biomedical industries. Discover Technologies is developing novel fabrication methods that allow the Plastic Muscles TM to be manufactured on a commercial scale. The Plastic Muscle TM transducers are capable of generating more than 0.5% bending strain at a peak strain rate of over 0.1 %/s with a 3 V input. Because the Plastic Muscles TM use an ionic liquid as a replacement solvent for water, they are able to operate in air for long periods of time. Also, the Plastic Muscles TM do not exhibit the characteristic "back relaxation" phenomenon that is common in water-swollen devices. The elastic modulus of the Plastic Muscle TM transducers is estimated to be 200 MPa and the maximum generated stress is estimated to be 1 MPa. Based on these values, the maximum blocked force at the tip of a 6 mm wide, 35 mm long actuator is estimated to be 19 mN. Modeling of the step response with an exponential series reveals nonlinearity in the transducers' behavior.
FOXO Regulates Organ-Specific Phenotypic Plasticity In Drosophila
Tang, Hui Yuan; Smith-Caldas, Martha S. B.; Driscoll, Michael V.; Salhadar, Samy; Shingleton, Alexander W.
2011-01-01
Phenotypic plasticity, the ability for a single genotype to generate different phenotypes in response to environmental conditions, is biologically ubiquitous, and yet almost nothing is known of the developmental mechanisms that regulate the extent of a plastic response. In particular, it is unclear why some traits or individuals are highly sensitive to an environmental variable while other traits or individuals are less so. Here we elucidate the developmental mechanisms that regulate the expression of a particularly important form of phenotypic plasticity: the effect of developmental nutrition on organ size. In all animals, developmental nutrition is signaled to growing organs via the insulin-signaling pathway. Drosophila organs differ in their size response to developmental nutrition and this reflects differences in organ-specific insulin-sensitivity. We show that this variation in insulin-sensitivity is regulated at the level of the forkhead transcription factor FOXO, a negative growth regulator that is activated when nutrition and insulin signaling are low. Individual organs appear to attenuate growth suppression in response to low nutrition through an organ-specific reduction in FOXO expression, thereby reducing their nutritional plasticity. We show that FOXO expression is necessary to maintain organ-specific differences in nutritional-plasticity and insulin-sensitivity, while organ-autonomous changes in FOXO expression are sufficient to autonomously alter an organ's nutritional-plasticity and insulin-sensitivity. These data identify a gene (FOXO) that modulates a plastic response through variation in its expression. FOXO is recognized as a key player in the response of size, immunity, and longevity to changes in developmental nutrition, stress, and oxygen levels. FOXO may therefore act as a more general regulator of plasticity. These data indicate that the extent of phenotypic plasticity may be modified by changes in the expression of genes involved in signaling environmental information to developmental processes. PMID:22102829
Solute-Gas Equilibria in Multi-Organic Aqueous Systems
1981-11-30
THIS PAGK(*7@nDae~ Kht.Eero*g) Block 20 (cont.) --z Henry’s constants for selected organic solvents were determined at ionic strengths up to 1.0 M (KC1...equili- brium, batch stripping reactor. Data were fit to a regression equation. Henry’s constants for selected organic solvents were determined at ionic...organic systems. The presence of additional or- ganics (some perhaps not even strippable ) likely to be found along with a particular volatile should be
Ionic liquid electrolytes for dye-sensitized solar cells.
Gorlov, Mikhail; Kloo, Lars
2008-05-28
The potential of room-temperature molten salts (ionic liquids) as solvents for electrolytes for dye-sensitized solar cells has been investigated during the last decade. The non-volatility, good solvent properties and high electrochemical stability of ionic liquids make them attractive solvents in contrast to volatile organic solvents. Despite this, the relatively high viscosity of ionic liquids leads to mass-transport limitations. Here we review recent developments in the application of different ionic liquids as solvents or components of liquid and quasi-solid electrolytes for dye-sensitized solar cells.
Abdullayeva, Nazrin; Sankir, Mehmet
2017-01-01
By using an easy and effective method of depositing conjugated polymers (PEDOT:PSS) on flexible substrates, a new design for organic bioelectronic devices has been developed. The purpose was to build up a system that mimics the motion of neurotransmitters in the synaptic cleft by obtaining an electrical to chemical signal transport. Fourier transform infrared (FTIR) spectroscopy and Raman measurements have demonstrated that electrochemical overoxidation region which separates the pristine PEDOT:PSS electrodes and allows ionic conduction has been achieved successfully. The influence of both electrical and ionic conductivities on organic electronic ion pump (OEIP) performances has been studied. The ultimate goal was to achieve the highest equilibrium current density at the lowest applied voltage via enhancing the electrical conductivity of PEDOT:PSS and ionic conductivity of electrochemically overoxidized region. The highest equilibrium current density, which corresponds to 4.81 × 1017 number of ions of acetylcholine was about 41 μA cm−2 observed for the OEIP with the electrical conductivities of 54 S cm−1. This was a threshold electrical conductivity beyond which the OEIP performances were not changed much. Once Nafion™ has been applied for enhancing the ionic conductivity, the equilibrium current density increased about ten times and reached up to 408 μA cm−2. Therefore, it has been demonstrated that the OEIP performance mainly scales with the ionic conductivity. A straightforward method of producing organic bioelectronics is proposed here may provide a clue for their effortless mass production in the near future. PMID:28772946
NASA Astrophysics Data System (ADS)
Dutta, Rituraj; Kumar, Ashok
2016-10-01
Metal Organic Frameworks (MOFs) are mesoporous materials that can be treated as potential hosts for trapping guest molecules in their pores. Ion conduction and phase behavior dynamics of Ionic Liquids (ILs) can be controlled by tunable interactions of MOFs with the ILs. MOFs incorporated with ionic liquid can be dispersed in the polymers to synthesize polymer electrolyte nanocomposites with high ionic conductivity, electrochemical and thermal stability for applications in energy storage and conversion devices such as rechargeable Li-ion batteries. In the present work we have synthesized Cu-based MOF [Cu3(l,3,5-benzene tricarboxylate)2(H2O)] incorporated with the ionic liquid 1-Butyl-3-methylimidazolium bromide at different weight ratios of MOF and IL. The synthesized MOF-IL composites are dispersed in Poly (ethylene oxide) (PEO). Frequency dependent behavior of permittivity and dielectric loss of the nanocomposites depict the non-Debye dielectric relaxation mechanism. The room temperature Nyquist plots reveal decreasing bulk resistance upto 189 Ω with optimum ionic conductivity of 1.3×10-3S cm-1at maximum doping concentration of IL in the nanocomposite system.
Effect of chitosan ethers on fresh state properties of lime mortars
NASA Astrophysics Data System (ADS)
Vyšvařil, M.; Žižlavský, T.
2017-10-01
The fresh state properties of mortars are eminently important since determine the material workability and also have a great influence on its hardened state characteristics. In this paper, the behaviour of fresh lime mortars modified by etherified derivatives of chitosan (hydroxypropylchitosan (HPCH) and carboxymethylchitosan (CMCH)) is assessed with the purpose of exploring a new application of such derivatives as lime mortar admixtures. The rheological parameters (relative yield stress, consistency coefficient and fluidity index) and viscoelastic properties were correlated with flow table tests, relative density measurements, water retention abilities of mortars and air content in mortars. Results were seen to be strongly dependent on substituents of the chitosan. Non-ionic derivative (HPCH) had a plasticizing influence on the mortars; the ionic CMCH showed the thickening effect. The effect of chitosan ethers was found to be dosage-dependent. CMCH had low impact on water retention, while HPCH displayed high water retention capability. It was concluded, that the ionic derivative (CMCH) is very similar by its viscosity enhancing effect to starch ether.
Soil-Water Characteristic Curves of Red Clay treated by Ionic Soil Stabilizer
NASA Astrophysics Data System (ADS)
Cui, D.; Xiang, W.
2009-12-01
The relationship of red clay particle with water is an important factor to produce geological disaster and environmental damage. In order to reduce the role of adsorbed water of red clay in WuHan, Ionic Soil Stabilizer (ISS) was used to treat the red clay. Soil Moisture Equipment made in U.S.A was used to measure soil-water characteristic curve of red clay both in natural and stabilized conditions in the suction range of 0-500kPa. The SWCC results were used to interpret the red clay behavior due to stabilizer treatment. In addition, relationship were compared between the basic soil and stabilizer properties such as water content, dry density, liquid limit, plastic limit, moisture absorption rate and stabilizer dosages. The analysis showed that the particle density and specific surface area increase, the dehydration rate slows and the thickness of water film thins after treatment with Ionic Soil Stabilizer. After treatment with the ISS, the geological disasters caused by the adsorbed water of red clay can be effectively inhibited.
NASA Astrophysics Data System (ADS)
Lo Celso, Fabrizio; Triolo, Alessandro; Gontrani, Lorenzo; Russina, Olga
2018-06-01
One of the outstanding features of ionic liquids is their inherently hierarchical structural organization at mesoscopic spatial scales. Recently experimental and computational studies showed the fading of this feature when pressurising. Here we use simulations to show that this effect is not general: appropriate anion choice leads to an obstinate resistance against pressurization.
A computer program for geochemical analysis of acid-rain and other low-ionic-strength, acidic waters
Johnsson, P.A.; Lord, D.G.
1987-01-01
ARCHEM, a computer program written in FORTRAN 77, is designed primarily for use in the routine geochemical interpretation of low-ionic-strength, acidic waters. On the basis of chemical analyses of the water, and either laboratory or field determinations of pH, temperature, and dissolved oxygen, the program calculates the equilibrium distribution of major inorganic aqueous species and of inorganic aluminum complexes. The concentration of the organic anion is estimated from the dissolved organic concentration. Ionic ferrous iron is calculated from the dissolved oxygen concentration. Ionic balances and comparisons of computed with measured specific conductances are performed as checks on the analytical accuracy of chemical analyses. ARCHEM may be tailored easily to fit different sampling protocols, and may be run on multiple sample analyses. (Author 's abstract)
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.
Thermodynamics of interaction of ionic liquids with lipid monolayer.
Bhattacharya, G; Mitra, S; Mandal, P; Dutta, S; Giri, R P; Ghosh, S K
2018-06-01
Understanding the interaction of ionic liquids with cellular membrane becomes utterly important to comprehend the activities of these liquids in living organisms. Lipid monolayer formed at the air-water interface is employed as a model system to follow this interaction by investigating important thermodynamic parameters. The penetration kinetics of the imidazolium-based ionic liquid 1-decyl-3-methylimidazolium tetrafluoroborate ([DMIM][BF4]) into the zwitterionic 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) lipid layer is found to follow the Boltzmann-like equation that reveals the characteristic time constant which is observed to be the function of initial surface pressure. The enthalpy and entropy calculated from temperature-dependent pressure-area isotherms of the monolayer show that the added ionic liquids bring about a disordering effect in the lipid film. The change in Gibbs free energy indicates that an ionic liquid with longer chain has a far greater disordering effect compared to an ionic liquid with shorter chain. The differential scanning calorimetric measurement on a multilamellar vesicle system shows the main phase transition temperature to shift to a lower value, which, again, indicates the disordering effect of the ionic liquid on lipid membrane. All these studies fundamentally point out that, when ionic liquids interact with lipid molecules, the self-assembled structure of a cellular membrane gets perturbed, which may be the mechanism of these molecules having adverse effects on living organisms.
Use of ionic liquids as coordination ligands for organometallic catalysts
Li, Zaiwei [Moreno Valley, CA; Tang, Yongchun [Walnut, CA; Cheng,; Jihong, [Arcadia, CA
2009-11-10
Aspects of the present invention relate to compositions and methods for the use of ionic liquids with dissolved metal compounds as catalysts for a variety of chemical reactions. Ionic liquids are salts that generally are liquids at room temperature, and are capable of dissolving a many types of compounds that are relatively insoluble in aqueous or organic solvent systems. Specifically, ionic liquids may dissolve metal compounds to produce homogeneous and heterogeneous organometallic catalysts. One industrially-important chemical reaction that may be catalyzed by metal-containing ionic liquid catalysts is the conversion of methane to methanol.
Ionic Liquids Beyond Simple Solvents: Glimpses at the State of the Art in Organic Chemistry.
Kuchenbuch, Andrea; Giernoth, Ralf
2015-12-01
Within the last 25 years ionic liquids have written a tremendous success story, which is documented in a nearly uncountable amount of original research papers, reviews, and numerous applications in research and industry. These days, ionic liquids can be considered as a mature class of compounds for many different applications. Frequently, they are used as neoteric solvents for chemical tansformations, and the number of reviews on this field of research is huge. In this focused review, though, we are trying to evaluate the state of the art of ionic liquid chemistry beyond using them simply as solvents for chemical transformations. It is not meant to be a comprehensive overview on the topic; the choice of emphasis and examples rather refects the authors' personal view on the field. We are especially highlighting fields in which we believe the most fundamental developments within the next five years will take place: biomass processing, (chiral) ionic liquids from natural sources, biotransformations, and organic synthesis.
Novak, E; Jalarvo, N; Gupta, S; Hong, K; Förster, S; Egami, T; Ohl, M
2018-06-01
Plastic crystals are a promising candidate for solid state ionic conductors. In this work, quasielastic neutron scattering is employed to investigate the center of mass diffusive motions in two types of plastic crystalline cyclic alcohols: cyclohexanol and cyclooctanol. Two separate motions are observed which are attributed to long-range translational diffusion (α-process) and cage rattling (fast β-process). Residence times and diffusion coefficients are calculated for both processes, along with the confinement distances for the cage rattling. In addition, a binary mixture of these two materials is measured to understand how the dynamics change when a second type of molecule is added to the matrix. It is observed that, upon the addition of the larger cyclooctanol molecules into the cyclohexanol solution, the cage size decreases, which causes a decrease in the observed diffusion rates for both the α- and fast β-processes.
Polychlorinated biphenyls and organochlorine pesticides in plastics ingested by seabirds.
Colabuono, Fernanda Imperatrice; Taniguchi, Satie; Montone, Rosalinda Carmela
2010-04-01
The occurrence of plastic objects in the digestive tract was assessed in eight species of Procellariiformes collected in southern Brazil and the occurrence of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in the ingested plastics pellets and plastic fragments was evaluated. PCBs were detected in plastic pellets (491 ng g(-1)) and plastic fragments (243-418 ng g(-1)). Among the OCPs, p,p'-DDE had the highest concentrations, ranging from 68.0 to 99.0 ng g(-1). The occurrence of organic pollutants in post-consumer plastics supports the fact that plastics are an important source carrying persistent organic pollutants in the marine environment. Although transfer through the food chain may be the main source of exposure to POPs to seabirds, plastics could be an additional source for the organisms which ingest them, like Procellariiformes which are the seabirds most affected by plastic pollution. (c) 2010 Elsevier Ltd. All rights reserved.
Li, Yantao; Zhang, Daojun; Gai, Fangyuan; Zhu, Xingqi; Guo, Ya-nan; Ma, Tianliang; Liu, Yunling; Huo, Qisheng
2012-08-18
Metal-organic polyhedra (MOP) nanocages were successfully surface functionalized via ionic self-assembly and the ordered honeycomb architecture of the encapsulated MOP nanocages was also fabricated at the air/water surface. The results provide a novel synthetic method and membrane processing technique of amphiphilic MOP nanocages for various applications.
Mixed protonic and electronic conductors hybrid oxide synaptic transistors
NASA Astrophysics Data System (ADS)
Fu, Yang Ming; Zhu, Li Qiang; Wen, Juan; Xiao, Hui; Liu, Rui
2017-05-01
Mixed ionic and electronic conductor hybrid devices have attracted widespread attention in the field of brain-inspired neuromorphic systems. Here, mixed protonic and electronic conductor (MPEC) hybrid indium-tungsten-oxide (IWO) synaptic transistors gated by nanogranular phosphorosilicate glass (PSG) based electrolytes were obtained. Unique field-configurable proton self-modulation behaviors were observed on the MPEC hybrid transistor with extremely strong interfacial electric-double-layer effects. Temporally coupled synaptic plasticities were demonstrated on the MPEC hybrid IWO synaptic transistor, including depolarization/hyperpolarization, synaptic facilitation and depression, facilitation-stead/depression-stead behaviors, spiking rate dependent plasticity, and high-pass/low-pass synaptic filtering behaviors. MPEC hybrid synaptic transistors may find potential applications in neuron-inspired platforms.
NASA Astrophysics Data System (ADS)
Thasneema K., K.; Thayyil, M. Shahin; Krishna Kumar N., S.; Govindaraj, G.; Saheer, V. C.
2018-04-01
Usually ionic liquids consists of a large organic cation with low symmetry such as imidazolium, pyridinium, quaternary ammonium or phosponium etc combined with enormously wide range of inorganic or organic symmetric anion with melting point below 100. Ionic liquids existing in an extremely large number of possible ion pair combinations. It offers a very wide range of thermo physical properties led to the concept of designer solvents for specific applications. Due to the features of high chemical and thermal stability, low vapor pressure non flammability high ionic conductivity, and they show a good solvent ability towards a great variety of organic or inorganic compounds, ionic liquids have a widespread use in many areas such as batteries, fuel cell, solar cells, super capacitors etc. The main focus of this work is the study of molecular dynamics and conductivity relaxation of amorphous Trihexyl tetradecyl phosphonium dicyanamide ([P14,6,6,6][N(CN)2]) ionic liquid which is proved as a better electrolyte in super capacitors, over a wide frequency 10-2 Hz to 107 Hz and the temperature range between 123k and 265 k by means of Broadband Dielectric Spectroscopy. We observe alpha conductivity relaxation and secondary relaxation above and below Glass Transition Temperature. The experimental results were analyzed using electric modulus representation. The analysis emphasis the inter molecular interaction and the nature of glass forming system, whether it is fragile or strong system. The ionic liquid shows a fragile behavior and the fragility index m=123.59. TGA result of the sample exhibit a good resistance to thermal decomposition, up to 300°C.
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.
Lin, YuPo J.; Hestekin, Jamie; Arora, Michelle; St. Martin, Edward J.
2004-09-28
An electrodeionization method for continuously producing and or separating and/or concentrating ionizable organics present in dilute concentrations in an ionic solution while controlling the pH to within one to one-half pH unit method for continuously producing and or separating and/or concentrating ionizable organics present in dilute concentrations in an ionic solution while controlling the pH to within one to one-half pH unit.
Membrane separation of ionic liquid solutions
Campos, Daniel; Feiring, Andrew Edward; Majumdar, Sudipto; Nemser, Stuart
2015-09-01
A membrane separation process using a highly fluorinated polymer membrane that selectively permeates water of an aqueous ionic liquid solution to provide dry ionic liquid. Preferably the polymer is a polymer that includes polymerized perfluoro-2,2-dimethyl-1,3-dioxole (PDD). The process is also capable of removing small molecular compounds such as organic solvents that can be present in the solution. This membrane separation process is suitable for drying the aqueous ionic liquid byproduct from precipitating solutions of biomass dissolved in ionic liquid, and is thus instrumental to providing usable lignocellulosic products for energy consumption and other industrial uses in an environmentally benign manner.
Amino acid anions in organic ionic compounds. An ab initio study of selected ion pairs.
Benedetto, A; Bodo, E; Gontrani, L; Ballone, P; Caminiti, R
2014-03-06
The combination of amino acids in their deprotonated and thus anionic form with a choline cation gives origin to a new and potentially important class of organic ionic compounds. A series of such neutral ion pairs has been investigated by first principle methods. The results reveal intriguing structural motives as well as regular patterns in the charge distribution and predict a number of vibrational and optical properties that could guide the experimental investigation of these compounds. The replacement of choline with its phosphocholine analogue causes the spontaneous reciprocal neutralization of cations and anions, taking place through the transfer of a proton between the two ions. Systems of this kind, therefore, provide a wide and easily accessible playground to probe the ionic/polar transition in organic systems, while the easy transfer of H(+) among neutral and ionic species points to their potential application as proton conductors. The analysis of the ab initio data highlights similarities as well as discrepancies from the rigid-ions force-field picture and suggests directions for the improvement of empirical models.
Hamlin, Heather J; Marciano, Kathleen; Downs, Craig A
2015-11-01
Nonylphenol (NP) is a non-ionic surfactant used extensively in industrial applications, personal care products, and many plastics. We exposed marine orchid dottybacks (Pseudochromis fridmani) for 48h to either glass, Teflon, or two bags labeled as FDA food-grade polyethylene (PE1 and PE2) from different manufacturers. The PE2 bags leached high levels of NP into the contact water, which were taken up by the fish, and decreased short and long-term survival. Concentrations of NP that leached from the bags were consistent with 96h LC50 values determined in this study, indicating NP is the likely toxic agent. Despite being similarly labeled, the NP concentrations that leached from the bags and the resultant toxicity to the fish varied dramatically between manufacturers. This study highlights that some plastics, labeled as food-safe, can be highly toxic to aquatic animals, and could pose a greater threat to humans than previously realized. This study also highlights risks for aquatic animals exposed to increasing quantities of plastic waste. Copyright © 2015 Elsevier Ltd. All rights reserved.
Roviello, Valentina; Sabbah, Mohammed
2017-01-01
Bitter vetch protein films containing positively charged spermidine, alone or with low amounts of glycerol, showed high tensile strength that progressively decreased by increasing the plasticizer concentration. Accordingly, lower film elongation at break and higher Young’s module values were detected in the presence of the polyamine without or with small amounts of glycerol. These data suggest that spermidine not only acts as a plasticizer itself by ionically interacting with proteins, but that it also facilitates glycerol-dependent reduction of the intermolecular forces along the protein chains, consequently improving the film flexibility and extensibility. Thus, spermidine may be considered not only as a primary, but also as a secondary plasticizer because of its ability to enhance glycerol plasticizing performance. Such double behavior of the polyamine was confirmed by the film permeability tests, since spermidine increased the barrier properties to gases and water vapor, while glycerol emphasized this effect at low concentrations but led to its marked reversal at high concentrations. Film microscopic images also substantiated these findings, showing more compact, cohesive, and homogeneous matrices in all spermidine-containing films. PMID:29292733
Instant tough bonding of hydrogels for soft machines and electronics
Wirthl, Daniela; Pichler, Robert; Drack, Michael; Kettlguber, Gerald; Moser, Richard; Gerstmayr, Robert; Hartmann, Florian; Bradt, Elke; Kaltseis, Rainer; Siket, Christian M.; Schausberger, Stefan E.; Hild, Sabine; Bauer, Siegfried; Kaltenbrunner, Martin
2017-01-01
Introducing methods for instant tough bonding between hydrogels and antagonistic materials—from soft to hard—allows us to demonstrate elastic yet tough biomimetic devices and machines with a high level of complexity. Tough hydrogels strongly attach, within seconds, to plastics, elastomers, leather, bone, and metals, reaching unprecedented interfacial toughness exceeding 2000 J/m2. Healing of severed ionic hydrogel conductors becomes feasible and restores function instantly. Soft, transparent multilayered hybrids of elastomers and ionic hydrogels endure biaxial strain with more than 2000% increase in area, facilitating soft transducers, generators, and adaptive lenses. We demonstrate soft electronic devices, from stretchable batteries, self-powered compliant circuits, and autonomous electronic skin for triggered drug delivery. Our approach is applicable in rapid prototyping and in delicate environments inaccessible for extended curing and cross-linking. PMID:28691092
Instant tough bonding of hydrogels for soft machines and electronics.
Wirthl, Daniela; Pichler, Robert; Drack, Michael; Kettlguber, Gerald; Moser, Richard; Gerstmayr, Robert; Hartmann, Florian; Bradt, Elke; Kaltseis, Rainer; Siket, Christian M; Schausberger, Stefan E; Hild, Sabine; Bauer, Siegfried; Kaltenbrunner, Martin
2017-06-01
Introducing methods for instant tough bonding between hydrogels and antagonistic materials-from soft to hard-allows us to demonstrate elastic yet tough biomimetic devices and machines with a high level of complexity. Tough hydrogels strongly attach, within seconds, to plastics, elastomers, leather, bone, and metals, reaching unprecedented interfacial toughness exceeding 2000 J/m 2 . Healing of severed ionic hydrogel conductors becomes feasible and restores function instantly. Soft, transparent multilayered hybrids of elastomers and ionic hydrogels endure biaxial strain with more than 2000% increase in area, facilitating soft transducers, generators, and adaptive lenses. We demonstrate soft electronic devices, from stretchable batteries, self-powered compliant circuits, and autonomous electronic skin for triggered drug delivery. Our approach is applicable in rapid prototyping and in delicate environments inaccessible for extended curing and cross-linking.
Investigation of the tracers for plastic-enriched waste burning aerosols
NASA Astrophysics Data System (ADS)
Kumar, Sudhanshu; Aggarwal, Shankar G.; Gupta, Prabhat K.; Kawamura, Kimitaka
2015-05-01
To better identify the tracers for open-waste burning (OWB) aerosols, we have conducted aerosol sampling at 2 landfill sites, i.e., Okhla and Bhalswa in New Delhi. The metals such as, As, Cd, Sb and Sn, which have been observed almost negligible in remote aerosols, are found abundantly in these OWB aerosol samples (n = 26), i.e., 60 ± 65, 41 ± 53, 537 ± 847 and 1325 ± 1218 ng m-3, respectively. Samples (n = 20) collected at urban locations in New Delhi, i.e., at Employees' State Insurance (ESI) hospital and National Physical Laboratory (NPL) also show high abundances of these metals in the particles. Filter samples are also analyzed for water-soluble dicarboxylic acids (C2-C12) and related compounds (oxocarboxylic acids and α-dicarbonyls). Terephthalic acid (tPh) was found to account for more than 77% of total diacids determined in OWB aerosols. However, such a high abundance of tPh is not observed in aerosols collected at urban sites. Instead, phthalic acid (Ph) was found as the third/fourth most abundant diacid (∼3%) following C2 (>70%) and C4 (>12%) in these waste burning influenced urban aerosols. A possible secondary formation pathway of Ph by photo-degradation of phthalate ester (di-2-ethylhexyl phthalate) in plastic-waste burning aerosol is suggested. Ionic composition of OWB aerosols showed that Cl- is the most abundant ion (40 ± 8% of total ions determined). The correlation studies of the potential metals with the organic tracers of garbage burning, i.e., phthalic, isophthalic and terephthalic acids show that especially Sn can be used as marker for tracing the plastic-enriched waste burning aerosols.
Electrical and electrochemical studies on sodium ion-based gel polymer electrolytes
NASA Astrophysics Data System (ADS)
Isa, K. B. Md; Othman, L.; Hambali, D.; Osman, Z.
2017-09-01
Gel polymer electrolytes (GPEs) have captured great attention because of their unique properties such as good mechanical stability, high flexibility and high conductivity approachable to that of the liquid electrolytes. In this work, we have prepared sodium ion conducting gel polymer electrolyte (GPE) films consisting of polyvinylidenefluoride-co-hexafluoropropylene (PVdF-HFP) as a polymer host using the solution casting technique. Sodium trifluoromethane- sulfonate (NaCF3SO3) was used as an ionic salt and the mixture of ethylene carbonate (EC) and propylene carbonate (PC) as a plasticizing solvent. Impedance spectroscopy measurements were carried out to determine the ionic conductivity of the GPE films. The sample containing 20 wt.% of NaCF3SO3 salt exhibits the highest room temperature ionic conductivity of 2.50 × 10-3 S cm-1. The conductivity of the GPE films was found to depend on the salt concentration that added to the films. The ionic and cationic transference numbers of GPE films were estimated by DC polarization and the combination of AC and DC polarization method, respectively. The results had shown that both ionic and cationic transference numbers are consistent with the conductivity studies. The electrochemical stability of the GPE films was tested using linear sweep voltammetry (LSV) and the value of working voltage range appears to be high enough to be used as an electrolyte in sodium batteries. The cyclic voltammetry (CV) studies confirmed the sodium ion conduction in the GPE films.
Surfactants have multi-fold effects on skin barrier function.
Lemery, Emmanuelle; Briançon, Stéphanie; Chevalier, Yves; Oddos, Thierry; Gohier, Annie; Boyron, Olivier; Bolzinger, Marie-Alexandrine
2015-01-01
The stratum corneum (SC) is responsible for the barrier properties of the skin and the role of intercorneocyte skin lipids, particularly their structural organization, in controlling SC permeability is acknowledged. Upon contacting the skin, surfactants interact with the SC components leading to barrier damage. To improve knowledge of the effect of several classes of surfactant on skin barrier function at three different levels. The influence of treatments of human skin explants with six non-ionic and four ionic surfactant solutions on the physicochemical properties of skin was investigated. Skin surface wettability and polarity were assessed through contact angle measurements. Infrared spectroscopy allowed monitoring the SC lipid organization. The lipid extraction potency of surfactants was evaluated thanks to HPLC-ELSD assays. One anionic and one cationic surfactant increased the skin polarity by removing the sebaceous and epidermal lipids and by disturbing the organization of the lipid matrix. Another cationic surfactant displayed a detergency effect without disturbing the skin barrier. Several non-ionic surfactants disturbed the lipid matrix organization and modified the skin wettability without any extraction of the skin lipids. Finally two non-ionic surfactants did not show any effect on the investigated parameters or on the skin barrier. The polarity, the organization of the lipid matrix and the lipid composition of the skin allowed describing finely how surfactants can interact with the skin and disturb the skin barrier function.
Ionic strength-induced formation of smectite quasicrystals enhances nitroaromatic compound sorption.
Li, Hui; Pereira, Tanya R; Teppen, Brian J; Laird, David A; Johnston, Cliff T; Boyd, Stephen A
2007-02-15
Sorption of organic contaminants by soils is a determinant controlling their transport and fate in the environment. The influence of ionic strength on nitroaromatic compound sorption by K+- and Ca2+ -saturated smectite was examined. Sorption of 1,3-dinitrobenzene by K-smectite increased as KCl ionic strength increased from 0.01 to 0.30 M. In contrast, sorption by Ca-smectite at CaCl2 ionic strengths of 0.015 and 0.15 M remained essentially the same. The "salting-out" effect on the decrease of 1,3-dinitrobenzene aqueous solubility within this ionic strength range was <1.5% relative to the solubility in pure water. This decrease of solubility is insufficient to account for the observed increase of sorption by K-smectite with increasing KCl ionic strength. X-ray diffraction patterns and light absorbance of K-clay suspensions indicated the aggregation of clay particles and the formation of quasicrystal structures as KCI ionic strength increased. Sorption enhancement is attributed to the formation of better-ordered K-clay quasicrystals with reduced interlayer distances rather than to the salting-out effect. Dehydration of 1,3-dinitrobenzene is apparently a significant driving force for sorption, and we show for the first time that sorption of small, planar, neutral organic molecules, namely, 1,3-dinitrobenzene, causes previously expanded clay interlayers to dehydrate and collapse in aqueous suspension.
Computer Simulation Study of Graphene Oxide Supercapacitors: Charge Screening Mechanism.
Park, Sang-Won; DeYoung, Andrew D; Dhumal, Nilesh R; Shim, Youngseon; Kim, Hyung J; Jung, YounJoon
2016-04-07
Graphene oxide supercapacitors in the parallel plate configuration are studied via molecular dynamics (MD) simulations. The full range of electrode oxidation from 0 to 100% is examined by oxidizing the graphene surface with hydroxyl groups. Two different electrolytes, 1-ethyl-3-methylimidazolium tetrafluoroborate (EMI(+)BF4(-)) as an ionic liquid and its 1.3 M solution in acetonitrile as an organic electrolyte, are considered. While the area-specific capacitance tends to decrease with increasing electrode oxidation for both electrolytes, its details show interesting differences between the organic electrolyte and ionic liquid, including the extent of decrease. For detailed insight into these differences, the screening mechanisms of electrode charges by electrolytes and their variations with electrode oxidation are analyzed with special attention paid to the aspects shared by and the contrasts between the organic electrolyte and ionic liquid.
IMPROVED SYNTHESIS OF ROOM TEMPERATURE IONIC LIQUIDS
Room temperature ionic liquids (RTILs), molten salts comprised of N-alkylimidazolium cations and various anions, have received significant attention due to their commercial potential in a variety of chemical applications especially as substitutes for conventional volatile organic...
NASA Astrophysics Data System (ADS)
Chondroudis, Konstantinos; Mitzi, David B.
2000-01-01
The conversion of two neutral dye molecules (D) to ionic salts (H2N-D-NH2ṡ2HX) and their utilization as emitting layers in organic light-emitting diodes (OLEDs) is described. The dye salts, AEQTṡ2HCl and APTṡ2HCl, can be deposited as amorphous films using conventional evaporation techniques. X-ray diffraction and scanning electron microscopy analysis, coupled with thermal annealing studies, demonstrate the resistance of the films to crystallization. This stability is attributed to strong ionic forces between the relatively rigid molecules. OLEDs incorporating such salts for emitting layers exhibit better thermal stability compared with devices made from the corresponding neutral dyes (H2N-D-NH2). These results suggest that ionic salts may more generally enable the formation of thermally stable, amorphous emitting, and charge transporting layers.
NASA Astrophysics Data System (ADS)
Mohapatra, Namrata; Tønnesen, Jan; Vlachos, Andreas; Kuner, Thomas; Deller, Thomas; Nägerl, U. Valentin; Santamaria, Fidel; Jedlicka, Peter
2016-03-01
Cl- plays a crucial role in neuronal function and synaptic inhibition. However, the impact of neuronal morphology on the diffusion and redistribution of intracellular Cl- is not well understood. The role of spines in Cl- diffusion along dendritic trees has not been addressed so far. Because measuring fast and spatially restricted Cl- changes within dendrites is not yet technically possible, we used computational approaches to predict the effects of spines on Cl- dynamics in morphologically complex dendrites. In all morphologies tested, including dendrites imaged by super-resolution STED microscopy in live brain tissue, spines slowed down longitudinal Cl- diffusion along dendrites. This effect was robust and could be observed in both deterministic as well as stochastic simulations. Cl- extrusion altered Cl- diffusion to a much lesser extent than the presence of spines. The spine-dependent slowing of Cl- diffusion affected the amount and spatial spread of changes in the GABA reversal potential thereby altering homosynaptic as well as heterosynaptic short-term ionic plasticity at GABAergic synapses in dendrites. Altogether, our results suggest a fundamental role of dendritic spines in shaping Cl- diffusion, which could be of relevance in the context of pathological conditions where spine densities and neural excitability are perturbed.
Pollutants in Plastics within the North Pacific Subtropical Gyre.
Chen, Qiqing; Reisser, Julia; Cunsolo, Serena; Kwadijk, Christiaan; Kotterman, Michiel; Proietti, Maira; Slat, Boyan; Ferrari, Francesco F; Schwarz, Anna; Levivier, Aurore; Yin, Daqiang; Hollert, Henner; Koelmans, Albert A
2018-01-16
Here we report concentrations of pollutants in floating plastics from the North Pacific accumulation zone (NPAC). We compared chemical concentrations in plastics of different types and sizes, assessed ocean plastic potential risks using sediment quality criteria, and discussed the implications of our findings for bioaccumulation. Our results suggest that at least a fraction of the NPAC plastics is not in equilibrium with the surrounding seawater. For instance, "hard plastic" samples had significantly higher PBDE concentrations than "nets and ropes" samples, and 29% of them had PBDE composition similar to a widely used flame-retardant mixture. Our findings indicate that NPAC plastics may pose a chemical risk to organisms as 84% of the samples had at least one chemical exceeding sediment threshold effect levels. Furthermore, our surface trawls collected more plastic than biomass (180 times on average), indicating that some NPAC organisms feeding upon floating particles may have plastic as a major component of their diets. If gradients for pollutant transfer from NPAC plastic to predators exist (as indicated by our fugacity ratio calculations), plastics may play a role in transferring chemicals to certain marine organisms.
Yu, Huanan; Xu, Dongdong; Xu, Qun
2015-08-28
A hierarchical meso- and microporous metal-organic framework (MOF) was facilely fabricated in an ionic liquid (IL)/supercritical CO2 (SC CO2)/surfactant emulsion system. Notably, CO2 exerts a dual effect during the synthesis; that is, CO2 droplets act as a template for the cores of nanospheres while CO2-swollen micelles induce mesopores on nanospheres.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Lonergan, Mark
Final technical report for Conjugated ionomers for photovoltaic applications, electric field driven charge separation in organic photovoltaics. The central goal of the work we completed was been to understand the photochemical and photovoltaic properties of ionically functionalized conjugated polymers (conjugated ionomers or polyelectrolytes) and energy conversion systems based on them. We primarily studied two classes of conjugated polymer interfaces that we developed based either upon undoped conjugated polymers with an asymmetry in ionic composition (the ionic junction) or doped conjugated polymers with an asymmetry in doping type (the p-n junction). The materials used for these studies have primarily been themore » polyacetylene ionomers. We completed a detailed study of p-n junctions with systematically varying dopant density, photochemical creation of doped junctions, and experimental and theoretical work on charge transport and injection in polyacetylene ionomers. We have also completed related work on the use of conjugated ionomers as interlayers that improve the efficiency or organic photovoltaic systems and studied several important aspects of the chemistry of ionically functionalized semiconductors, including mechanisms of so-called "anion-doping", the formation of charge transfer complexes with oxygen, and the synthesis of new polyfluorene polyelectrolytes. We also worked worked with the Haley group at the University of Oregon on new indenofluorene-based organic acceptors.« less
Facile and scalable fabrication of polymer-ceramic composite electrolyte with high ceramic loadings
NASA Astrophysics Data System (ADS)
Pandian, Amaresh Samuthira; Chen, X. Chelsea; Chen, Jihua; Lokitz, Bradley S.; Ruther, Rose E.; Yang, Guang; Lou, Kun; Nanda, Jagjit; Delnick, Frank M.; Dudney, Nancy J.
2018-06-01
Solid state electrolytes are a promising alternative to flammable liquid electrolytes for high-energy lithium battery applications. In this work polymer-ceramic composite electrolyte membrane with high ceramic loading (greater than 60 vol%) is fabricated using a model polymer electrolyte poly(ethylene oxide) + lithium trifluoromethane sulfonate and a lithium-conducting ceramic powder. The effects of processing methods, choice of plasticizer and varying composition on ionic conductivity of the composite electrolyte are thoroughly investigated. The physical, structural and thermal properties of the composites are exhaustively characterized. We demonstrate that aqueous spray coating followed by hot pressing is a scalable and inexpensive technique to obtain composite membranes that are amazingly dense and uniform. The ionic conductivity of composites fabricated using this protocol is at least one order of magnitude higher than those made by dry milling and solution casting. The introduction of tetraethylene glycol dimethyl ether further increases the ionic conductivity. The composite electrolyte's interfacial compatibility with metallic lithium and good cyclability is verified by constructing lithium symmetrical cells. A remarkable Li+ transference number of 0.79 is discovered for the composite electrolyte.
Mixtures of amino-acid based ionic liquids and water.
Chaban, Vitaly V; Fileti, Eudes Eterno
2015-09-01
New ionic liquids (ILs) involving increasing numbers of organic and inorganic ions are continuously being reported. We recently developed a new force field; in the present work, we applied that force field to investigate the structural properties of a few novel imidazolium-based ILs in aqueous mixtures via molecular dynamics (MD) simulations. Using cluster analysis, radial distribution functions, and spatial distribution functions, we argue that organic ions (imidazolium, deprotonated alanine, deprotonated methionine, deprotonated tryptophan) are well dispersed in aqueous media, irrespective of the IL content. Aqueous dispersions exhibit desirable properties for chemical engineering. The ILs exist as ion pairs in relatively dilute aqueous mixtures (10 mol%), while more concentrated mixtures feature a certain amount of larger ionic aggregates.
Ionic strength and DOC determinations from various freshwater sources to the San Francisco Bay
Hunter, Y.R.; Kuwabara, J.S.
1994-01-01
An exact estimation of dissolved organic carbon (DOC) within the salinity gradient of zinc and copper metals is significant in understanding the limit to which DOC could influence metal speciation. A low-temperature persulfate/oxygen/ultraviolet wet oxidation procedure was utilized for analyzing DOC samples adapted for ionic strength from major freshwater sources of the northern and southern regions of San Francisco Bay. The ionic strength of samples was modified with a chemically defined seawater medium up to 0.7M. Based on the results, a minimum effect of ionic strength on oxidation proficiency for DOC sources to the Bay over an ionic strength gradient of 0.0 to 0.7 M was observed. There was no major impacts of ionic strength on two Suwanee River fulvic acids. In general, the noted effects associated with ionic strength were smaller than the variances seen in the aquatic environment between high- and low-temperature methods.
Fujimoto, Takuya; Miyoshi, Yasuhito; Matsushita, Michio M; Awaga, Kunio
2011-05-28
We studied a complementary organic inverter consisting of a p-type semiconductor, metal-free phthalocyanine (H(2)Pc), and an n-type semiconductor, tetrakis(thiadiazole)porphyrazine (H(2)TTDPz), operated through the ionic-liquid gate dielectrics of N,N-diethyl-N-methyl(2-methoxyethyl)ammonium bis(trifluoromethylsulfonyl)imide (DEME-TFSI). This organic inverter exhibits high performance with a very low operation voltage below 1.0 V and a dynamic response up to 20 Hz. © The Royal Society of Chemistry 2011
Nano-plastics in the aquatic environment.
Mattsson, K; Hansson, L-A; Cedervall, T
2015-10-01
The amount of plastics released to the environment in modern days has increased substantially since the development of modern plastics in the early 1900s. As a result, concerns have been raised by the public about the impact of plastics on nature and on, specifically, aquatic wildlife. Lately, much attention has been paid to macro- and micro-sized plastics and their impact on aquatic organisms. However, micro-sized plastics degrade subsequently into nano-sizes whereas nano-sized particles may be released directly into nature. Such particles have a different impact on aquatic organisms than larger pieces of plastic due to their small size, high surface curvature, and large surface area. This review describes the possible sources of nano-sized plastic, its distribution and behavior in nature, the impact of nano-sized plastic on the well-being of aquatic organisms, and the difference of impact between nano- and micro-sized particles. We also identify research areas which urgently need more attention and suggest experimental methods to obtain useful data.
New electrolytes for aluminum production: Ionic liquids
NASA Astrophysics Data System (ADS)
Zhang, Mingming; Kamavarum, Venkat; Reddy, Ramana G.
2003-11-01
In this article, the reduction, refining/recycling, and electroplating of aluminum from room-temperature molten salts are reviewed. In addition, the characteristics of several non-conventional organic solvents, electrolytes, and molten salts are evaluated, and the applicability of these melts for production of aluminum is discussed with special attention to ionic liquids. Also reviewed are electrochemical processes and conditions for electrodeposition of aluminum using ionic liquids at near room temperatures.
NASA Astrophysics Data System (ADS)
Minnick, David L.
Lignocellulose is the most abundant biopolymer on earth making it a promising feedstock for the production of renewable chemicals and fuels. However, utilization of biomass remains a challenge as recalcitrance of cellulose and hemicellulose hinder separation and conversion of these carbohydrates. For instance, the complex inter- and intra- molecular hydrogen bonding network of cellulose renders it insoluble in nearly all aqueous and organic solvents. Alternatively, select ionic liquids (ILs) dissolve significant quantities. Through an ionic liquid mediated dissolution and precipitation process cellulose crystallinity is significantly reduced consequently enhancing subsequent chemical and biochemical reaction processes. Therefore, understanding the thermodynamics of ionic liquid - cellulose mixtures is imperative to developing an IL based biomass processing system. This dissertation illustrates solid-liquid phase equilibrium results for the dissolution and precipitation of cellulose in various IL/cosolvent, IL/antisolvent, and IL/mixed solvent systems with the ionic liquid 1-ethyl-3-methylimidazolium diethyl phosphate ([EMIm][DEP]). Molecular interactions between the ionic liquid, organic solvents, and cellulose are assessed by spectroscopic techniques including Kamlet-Taft solvatochromic analysis, FTIR, and NMR. Additionally, this dissertation discusses how preferential solvation of the IL cation and anion by co- and anti-solvents impact the ability of IL ions to interact with cellulose thus affecting the cellulose dissolution capacity of the various IL-solvent mixtures.
Cloud-Based Applications for Organizing and Reviewing Plastic Surgery Content
Luan, Anna; Momeni, Arash; Lee, Gordon K.
2015-01-01
Cloud-based applications including Box, Dropbox, Google Drive, Evernote, Notability, and Zotero are available for smartphones, tablets, and laptops and have revolutionized the manner in which medical students and surgeons read and utilize plastic surgery literature. Here we provide an overview of the use of Cloud computing in practice and propose an algorithm for organizing the vast amount of plastic surgery literature. Given the incredible amount of data being produced in plastic surgery and other surgical subspecialties, it is prudent for plastic surgeons to lead the process of providing solutions for the efficient organization and effective integration of the ever-increasing data into clinical practice. PMID:26576208
Telling, Jon; Anesio, Alexandre M.; Tranter, Martyn; Fountain, Andrew G.; Nylen, Thomas; Hawkings, Jon; Singh, Virendra B.; Kaur, Preeti; Musilova, Michaela; Wadham, Jemma L.
2014-01-01
The seasonal melting of ice entombed cryoconite holes on McMurdo Dry Valley glaciers provides oases for life in the harsh environmental conditions of the polar desert where surface air temperatures only occasionally exceed 0°C during the Austral summer. Here we follow temporal changes in cryoconite hole biogeochemistry on Canada Glacier from fully frozen conditions through the initial stages of spring thaw toward fully melted holes. The cryoconite holes had a mean isolation age from the glacial drainage system of 3.4 years, with an increasing mass of aqueous nutrients (dissolved organic carbon, total nitrogen, total phosphorus) with longer isolation age. During the initial melt there was a mean nine times enrichment in dissolved chloride relative to mean concentrations of the initial frozen holes indicative of an ionic pulse, with similar mean nine times enrichments in nitrite, ammonium, and dissolved organic matter. Nitrate was enriched twelve times and dissolved organic nitrogen six times, suggesting net nitrification, while lower enrichments for dissolved organic phosphorus and phosphate were consistent with net microbial phosphorus uptake. Rates of bacterial production were significantly elevated during the ionic pulse, likely due to the increased nutrient availability. There was no concomitant increase in photosynthesis rates, with a net depletion of dissolved inorganic carbon suggesting inorganic carbon limitation. Potential nitrogen fixation was detected in fully melted holes where it could be an important source of nitrogen to support microbial growth, but not during the ionic pulse where nitrogen availability was higher. This study demonstrates that ionic pulses significantly alter the timing and magnitude of microbial activity within entombed cryoconite holes, and adds credence to hypotheses that ionic enrichments during freeze-thaw can elevate rates of microbial growth and activity in other icy habitats, such as ice veins and subglacial regelation zones. PMID:25566210
Telling, Jon; Anesio, Alexandre M; Tranter, Martyn; Fountain, Andrew G; Nylen, Thomas; Hawkings, Jon; Singh, Virendra B; Kaur, Preeti; Musilova, Michaela; Wadham, Jemma L
2014-01-01
The seasonal melting of ice entombed cryoconite holes on McMurdo Dry Valley glaciers provides oases for life in the harsh environmental conditions of the polar desert where surface air temperatures only occasionally exceed 0°C during the Austral summer. Here we follow temporal changes in cryoconite hole biogeochemistry on Canada Glacier from fully frozen conditions through the initial stages of spring thaw toward fully melted holes. The cryoconite holes had a mean isolation age from the glacial drainage system of 3.4 years, with an increasing mass of aqueous nutrients (dissolved organic carbon, total nitrogen, total phosphorus) with longer isolation age. During the initial melt there was a mean nine times enrichment in dissolved chloride relative to mean concentrations of the initial frozen holes indicative of an ionic pulse, with similar mean nine times enrichments in nitrite, ammonium, and dissolved organic matter. Nitrate was enriched twelve times and dissolved organic nitrogen six times, suggesting net nitrification, while lower enrichments for dissolved organic phosphorus and phosphate were consistent with net microbial phosphorus uptake. Rates of bacterial production were significantly elevated during the ionic pulse, likely due to the increased nutrient availability. There was no concomitant increase in photosynthesis rates, with a net depletion of dissolved inorganic carbon suggesting inorganic carbon limitation. Potential nitrogen fixation was detected in fully melted holes where it could be an important source of nitrogen to support microbial growth, but not during the ionic pulse where nitrogen availability was higher. This study demonstrates that ionic pulses significantly alter the timing and magnitude of microbial activity within entombed cryoconite holes, and adds credence to hypotheses that ionic enrichments during freeze-thaw can elevate rates of microbial growth and activity in other icy habitats, such as ice veins and subglacial regelation zones.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Chew, K. W.; Chen, S. S.; Pang, W. L.
The effects of Lithium triflate salt (LiCF{sub 3}SO{sub 3}), on the poly (methyl methacrylate)(PMMA)-based solid polymer electrolytes plasticized with propylene carbonate (PC) solvated in Tetrahydrofuran (THF) have been studied through a.c impedance spectroscopy and infrared spectroscopy. Lithium triflate was incorporated into the predetermined PMMA/PC system that has the highest value of ionic conductivity. In current investigations, four combination systems: Pure PMMA, (PMMA+PC) systems, (PMMA+LiCF{sub 3}SO{sub 3}) and (PMMA+PC+LiCF{sub 3}SO{sub 3}) systems were prepared using the solution cast method. Solutions were stirred for numerous hours to obtain a homogenous solution before it is poured into the petri dishes under ambient temperaturemore » to form the solid electrolyte thin film. The films were then removed from petri discs and transferred into the dessicator for further drying prior to the different tests. From the characterization done through the a.c impedance spectroscopy, the highest room temperature ionic conductivity in the pure PMMA sample, (PMMA+PC) system and (PMMA+LiCF{sub 3}SO{sub 3}) system is 2.83x10{sup -12} Scm{sup -1}, 4.39x10{sup -11} Scm{sup -1} and 3.93x10{sup -6} Scm{sup -1} respectively. The conductivity for (PMMA+PC+LiCF{sub 3}SO{sub 3}) system was obtained with the 30 wt% of lithium triflate, which is 2.48x10{sup -5} Scm{sup -1}. Infrared spectroscopy shows that complexation occurred between the polymer and the plasticizer, and the polymer and plasticizer and salt. The interactions have been studied in the C=O band, C-O-C band and the O-CH{sub 3} band.« less
Block Copolymers and Ionic Liquids: A New Class of Functional Nanocomposites
NASA Astrophysics Data System (ADS)
Lodge, Timothy
2009-03-01
Block copolymers provide a remarkably versatile platform for achieving desired nanostructures by self-assembly, with lengthscales varying from a few nanometers up to several hundred nanometers. Ionic liquids are an emerging class of solvents, with an appealing set of physical attributes. These include negligible vapor pressure, high chemical and thermal stability, tunable solvation properties, high ionic conductivity, and wide electrochemical windows. For various applications it will be necessary to solidify the ionic liquid into particular spatial arrangements, such as membranes or gels, or to partition the ionic liquid in coexisting phases, such as microemulsions and micelles. One example includes formation of spherical, cylindrical, and vesicular micelles by poly(butadiene-b-ethylene oxide) and poly(styrene-b-methylmethacrylate) in the common hydrophobic ionic liquids [BMI][PF6] and [EMI][TFSI]. This work has been extended to the formation of reversible micelle shuttles between ionic liquids and water, whereby entire micelles transfer from one phase to the other, reversibly, depending on temperature and solvent quality. Formation of ion gels has been achieved by self-assembly of poly(styrene-b-ethylene oxide-b-styrene) triblocks in ionic liquids, and by the thermoreversible system poly(N-isopropylacrylamide-b-ethylene oxide-b-N-isopropylacrylamide), using as little as 4% copolymer. Further, these gels have been shown to be remarkably effective as gate dielectrics in organic thin film transistors. The remarkably high capacitance of the ion gels (> 10 μF/cm^2) supports a very high carrier density in an organic semiconductor such as poly(3-hexylthiophene), leading to milliamp currents for low applied voltages. Furthermore, the rapid mobility of the ions enables switching speeds approaching 10 kHz, orders of magnitude higher than achievable with other polymer-based dielectrics such as PEO/LiClO4. Finally, we have shown that ordered nanostructures of block copolymers plus ionic liquids show the characteristic self-assembly properties of strongly-segregated systems. Prospects for anisotropic ionic conductivity are also being explored.
40 CFR 52.777 - Control strategy: photochemical oxidants (hydrocarbons).
Code of Federal Regulations, 2013 CFR
2013-07-01
... lithography operations, business plastics, automotive plastics, and synthetic organic chemical manufacturing..., automotive plastics, and synthetic organic chemical manufacturing industries (SOCMI) batch processes... Michigan area, and an agreed order between U.S. Steel (currently USX Corporation) and the IDEM signed by...
40 CFR 52.777 - Control strategy: photochemical oxidants (hydrocarbons).
Code of Federal Regulations, 2012 CFR
2012-07-01
... lithography operations, business plastics, automotive plastics, and synthetic organic chemical manufacturing..., automotive plastics, and synthetic organic chemical manufacturing industries (SOCMI) batch processes... Michigan area, and an agreed order between U.S. Steel (currently USX Corporation) and the IDEM signed by...
Gao, Jiajia; Wang, Hui; Qu, Jingang; Wang, Huili; Wang, Xuedong
2017-01-15
In traditional ionic liquids (ILs)-based microextraction, ILs are often used as extraction and dispersive solvents; however, their functional effects are not fully utilized. Herein, we developed a novel ionic liquid 1-butyl-3-methylimidazolium naphthoic acid salt ([C4MIM][NPA]) with strong acidity. It was used as a mixed dispersive solvent with conventional [C2MIM][BF4] in "functionalized ionic liquid-based non-organic solvent microextraction (FIL-NOSM)" for determination of tetracycline antibiotics (TCs) in milk and eggs. Utilization of [C4MIM][NPA] in FIL-NOSM method increased extraction recoveries (ERs) of TCs by more than 20% and eliminated the pH adjustment step because of its strong acidity. Under optimized conditions based on central composite design, the ERs of four TCs were 94.1-102.1%, and the limitsofdetection were 0.08-1.12μgkg(-1) in milk and egg samples. This proposed method provides high extraction efficiency, less pretreatment time and requires non-organic solvents for determination of trace TC concentrations in complex animal-based food matrices. Copyright © 2016 Elsevier Ltd. All rights reserved.
Zeindlhofer, Veronika; Schröder, Christian
2018-06-01
Based on their tunable properties, ionic liquids attracted significant interest to replace conventional, organic solvents in biomolecular applications. Following a Gartner cycle, the expectations on this new class of solvents dropped after the initial hype due to the high viscosity, hydrolysis, and toxicity problems as well as their high cost. Since not all possible combinations of cations and anions can be tested experimentally, fundamental knowledge on the interaction of the ionic liquid ions with water and with biomolecules is mandatory to optimize the solvation behavior, the biodegradability, and the costs of the ionic liquid. Here, we report on current computational approaches to characterize the impact of the ionic liquid ions on the structure and dynamics of the biomolecule and its solvation layer to explore the full potential of ionic liquids.
Calcium, Synaptic Plasticity and Intrinsic Homeostasis in Purkinje Neuron Models
Achard, Pablo; De Schutter, Erik
2008-01-01
We recently reproduced the complex electrical activity of a Purkinje cell (PC) with very different combinations of ionic channel maximum conductances, suggesting that a large parameter space is available to homeostatic mechanisms. It has been hypothesized that cytoplasmic calcium concentrations control the homeostatic activity sensors. This raises many questions for PCs since in these neurons calcium plays an important role in the induction of synaptic plasticity. To address this question, we generated 148 new PC models. In these models the somatic membrane voltages are stable, but the somatic calcium dynamics are very variable, in agreement with experimental results. Conversely, the calcium signal in spiny dendrites shows only small variability. We demonstrate that this localized control of calcium conductances preserves the induction of long-term depression for all models. We conclude that calcium is unlikely to be the sole activity-sensor in this cell but that there is a strong relationship between activity homeostasis and synaptic plasticity. PMID:19129937
Dai, Sheng [Knoxville, TN; Luo, Huimin [Knoxville, TN
2008-09-09
Ionic compounds which are liquids at room temperature are formed by the method of mixing a neutral organic liqand with the salt of a metal cation and its conjugate anion. The liquids are hydrophobic, conductive and stable and have uses as solvents and in electrochemical devices.
Dai, Sheng [Knoxville, TN; Luo, Huimin [Knoxville, TN
2011-11-01
Ionic compounds which are liquids at room temperature are formed by the method of mixing a neutral organic ligand with the salt of a metal cation and its conjugate anion. The liquids are hydrophobic, conductive and stable and have uses as solvents and in electrochemical devices.
An Ionic Liquid Reaction and Separation Process for Production of Hydroxymethylfurfural from Sugars
DOE Office of Scientific and Technical Information (OSTI.GOV)
Liu, Wei; Zheng, Feng; Li, Joanne
2014-01-01
There has been world-wide interest to making plastics out of renewable biomass feedstock for recent years. Hydroxymethylfurfural (HMF) is viewed as an attractive alternate to terephthalic acid (TPA) for production of polyesters (PET) and polyamides. Conversion of sugars into HMF has been studied in numerous publications. In this work, a complete ionic liquid reaction and separation process is presented for nearly stoichiometric conversion of fructose into HMF. Different adsorbent materials are evaluated and silicalite material is demonstrated effective for isolation of 99% pure HMF from actual ionic liquid reaction mixtures and for recovery of the un-converted sugars and reaction intermediatemore » along with the ionic liquid. Membrane-coated silicalite particles are prepared and studied for a practical adsorption process operated at low pressure drops but with separation performances comparable or better than the powder material. Complete conversion of fresh fructose feed into HMF in the recycled ionic liquid is shown under suitable reaction conditions. Stability of HMF product is characterized. A simplified process flow diagram is proposed based on these research results, and the key equipment such as reactor and adsorbent bed is sized for a plant of 200,000 ton/year of fructose processing capacity. The proposed HMF production process is much simpler than the current paraxylene (PX) manufacturing process from petroleum oil, which suggests substantial reduction to the capital cost and energy consumption be possible. At the equivalent value to PX on the molar basis, there can be a large gross margin for HMF production from fructose and/or sugars.« less
Subianto, Surya; Mistry, Mayur K; Choudhury, Namita Roy; Dutta, Naba K; Knott, Robert
2009-06-01
A new type of supported liquid membrane was made by combining an ionic liquid (IL) with a Nafion membrane reinforced with multifunctional polyhedral oligomeric silsesquioxanes (POSSs) using a layer-by-layer strategy for anhydrous proton-exchange membrane (PEM) application. The POSS was functionalized by direct sulfonation, and the sulfonated POSS (S-POSS) was incorporated into Nafion 117 membranes by the infiltration method. The resultant hybrid membrane shows strong ionic interaction between the Nafion matrix and the multifunctional POSS, resulting in increased glass transition temperature and thermal stability at very low loadings of S-POSS (1%). The presence of S-POSS has also improved the proton conductivity especially at low humidities, where it shows a marked increase due to its confinement in the ionic domains and promotes water uptake by capillary condensation. In order to achieve anhydrous conductivity, the IL 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BMI-BTSI) was incorporated into these membranes to provide proton conduction in the absence of water. Although the incorporation of an IL shows a plasticizing effect on the Nafion membrane, the S-POSS composite membrane with an IL shows a higher modulus at high temperatures compared to Nafion 117 and a Nafion-IL membrane, with significantly higher proton conductivity (5 mS/cm at 150 degrees C with 20% IL). This shows the ability of the multifunctional POSS and IL to work symbiotically to achieve the desirable proton conductivity and mechanical properties of such membranes by enhancing the ionic interaction within the material.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Lian, Cheng; Univ. of California, Riverside, CA; Liu, Honglai
The ionophobicity effect of nanoporous electrodes on the capacitance and the energy storage capacity of nonaqueous-electrolyte supercapacitors is studied by means of the classical density functional theory (DFT). It has been hypothesized that ionophobic nanopores may create obstacles in charging, but they store energy much more efficiently than ionophilic pores. In this paper, we find that, for both ionic liquids and organic electrolytes, an ionophobic pore exhibits a charging behavior different from that of an ionophilic pore, and that the capacitance–voltage curve changes from a bell shape to a two-hump camel shape when the pore ionophobicity increases. For electric-double-layer capacitorsmore » containing organic electrolytes, an increase in the ionophobicity of the nanopores leads to a higher capacity for energy storage. Without taking into account the effects of background screening, the DFT predicts that an ionophobic pore containing an ionic liquid does not enhance the supercapacitor performance within the practical voltage ranges. However, by using an effective dielectric constant to account for ion polarizability, the DFT predicts that, like an organic electrolyte, an ionophobic pore with an ionic liquid is also able to increase the energy stored when the electrode voltage is beyond a certain value. We find that the critical voltage for an enhanced capacitance in an ionic liquid is larger than that in an organic electrolyte. Finally, our theoretical predictions provide further understanding of how chemical modification of porous electrodes affects the performance of supercapacitors.« less
40 CFR 414.11 - Applicability.
Code of Federal Regulations, 2013 CFR
2013-07-01
... ORGANIC CHEMICALS, PLASTICS, AND SYNTHETIC FIBERS General § 414.11 Applicability. (a) The provisions of... establishments that manufacture the organic chemicals, plastics, and synthetic fibers (OCPSF) products or product... Intermediates, Dyes, and Organic Pigments, (5) SIC 2869—Industrial Organic Chemicals, Not Elsewhere Classified...
40 CFR 414.11 - Applicability.
Code of Federal Regulations, 2012 CFR
2012-07-01
... ORGANIC CHEMICALS, PLASTICS, AND SYNTHETIC FIBERS General § 414.11 Applicability. (a) The provisions of... establishments that manufacture the organic chemicals, plastics, and synthetic fibers (OCPSF) products or product... Intermediates, Dyes, and Organic Pigments, (5) SIC 2869—Industrial Organic Chemicals, Not Elsewhere Classified...
40 CFR 414.11 - Applicability.
Code of Federal Regulations, 2014 CFR
2014-07-01
... ORGANIC CHEMICALS, PLASTICS, AND SYNTHETIC FIBERS General § 414.11 Applicability. (a) The provisions of... establishments that manufacture the organic chemicals, plastics, and synthetic fibers (OCPSF) products or product... Intermediates, Dyes, and Organic Pigments, (5) SIC 2869—Industrial Organic Chemicals, Not Elsewhere Classified...
40 CFR 414.11 - Applicability.
Code of Federal Regulations, 2011 CFR
2011-07-01
... ORGANIC CHEMICALS, PLASTICS, AND SYNTHETIC FIBERS General § 414.11 Applicability. (a) The provisions of... establishments that manufacture the organic chemicals, plastics, and synthetic fibers (OCPSF) products or product... Intermediates, Dyes, and Organic Pigments, (5) SIC 2869—Industrial Organic Chemicals, Not Elsewhere Classified...
PALLADIUM-CATALYZED OXIDATION OF STYRENE AND ALKENES IN PRESENCE OF IONIC LIQUIDS (WACKER REACTION)
The use of ionic liquids in various synthetic transformations is gaining significance due to the enhanced reaction rates, potential for recycling and compatibility with various organic compounds and organometallic catalysts. Palladium-catalyzed oxidation of styrene and other alk...
Ionic current rectification in organic solutions with quartz nanopipettes.
Yin, Xiaohong; Zhang, Shudong; Dong, Yitong; Liu, Shujuan; Gu, Jing; Chen, Ye; Zhang, Xin; Zhang, Xianhao; Shao, Yuanhua
2015-09-01
The study of behaviors of ionic current rectification (ICR) in organic solutions with quartz nanopipettes is reported. ICR can be observed even in organic solutions using quartz pipettes with diameters varied from several to dozens of nanometers, and the direction of ICR is quite different from the ICR observed in aqueous phase. The influences of pore size, electrolyte concentration, and surface charge on the ICR have been investigated carefully. Water in organic solutions affects the direction and extent of ICR significantly. Mechanisms about the formation of an electrical double layer (EDL) on silica in organic solutions with different amount of water have been proposed. An improved method, which can be employed to detect trace water in organic solutions, has been implemented based on Au ultramicroelectrodes with cathodic differential pulse stripping voltammetry.
Combustible ionic liquids by design: is laboratory safety another ionic liquid myth?
Smiglak, Marcin; Reichert, W Mathew; Holbrey, John D; Wilkes, John S; Sun, Luyi; Thrasher, Joseph S; Kirichenko, Kostyantyn; Singh, Shailendra; Katritzky, Alan R; Rogers, Robin D
2006-06-28
The non-flammability of ionic liquids (ILs) is often highlighted as a safety advantage of ILs over volatile organic compounds (VOCs), but the fact that many ILs are not flammable themselves does not mean that they are safe to use near fire and/or heat sources; a large group of ILs (including commercially available ILs) are combustible due to the nature of their positive heats of formation, oxygen content, and decomposition products.
Charge ordering in ionic fluids mediate repulsive surface interactions
NASA Astrophysics Data System (ADS)
Dasbiswas, Kinjal; Ludwig, Nicholas B.; Zhang, Hao; Talapin, Dmitri; Vaikuntanathan, Suri
Recent experiments on ionic fluids, such as surface force measurements in organic ionic liquids and the observation of colloidal stability in inorganic molten salts, suggest the presence of long-ranged repulsive forces. These cannot be explained within the classical Debye-Hückel theory for dilute electrolytes. We argue that such repulsive interactions can arise from long-range (several nm) charge density oscillations induced by a surface that preferentially binds one of the ionic species in an ionic fluid. We present a continuum theory that accounts for such charge layering based on a frustrated Ising model that incorporates both long-range Coulombic and short-range steric interactions. The mean-field analytic treatment qualitatively matches results from molecular simulations. A careful analysis of the ionic correlation functions arising from such charge ordering may also explain the long electrostatic screening lengths observed in various ionic fluids and their non-monotonic dependence on the electrolyte concentration. We acknowledge the University of Chicago for support.
Synthesis and characterization of ionomers as polymer electrolytes for energy conversion devices
NASA Astrophysics Data System (ADS)
Oh, Hyukkeun
Single-ion conducting electrolytes present a unique alternative to traditional binary salt conductors used in lithium-ion batteries. Secondary lithium batteries are considered as one of the leading candidates to replace the combustible engines in automotive technology, however several roadblocks are present which prevent their widespread commercialization. Power density, energy density and safety properties must be improved in order to enable the current secondary lithium battery technology to compete with existing energy technologies. It has been shown theoretically that single-ion electrolytes can eliminate the salt concentration gradient and polarization loss in the cell that develops in a binary salt system, resulting in substantial improvements in materials utilization for high power and energy densities. While attempts to utilize single-ion conducting electrolytes in lithium-ion battery systems have been made, the low ionic conductivities prevented the successful operation of the battery cells in ambient conditions. This work focuses on designing single-ion conducting electrolytes with high ionic conductivities and electrochemical and mechanical stability which enables the stable charge-discharge performance of battery cells. Perfluorosulfonate ionomers are known to possess exceptionally high ionic conductivities due to the electron-withdrawing effect caused by the C-F bonds which stabilizes the negative charge of the anion, leading to a large number of free mobile cations. The effect of perfluorinated sulfonic acid side chains on transport properties of proton exchange membrane polymers was examinated via a comparison of three ionomers, having different side chain structures and a similar polymer backbone. The three different side chain structures were aryl-, pefluoro alkyl-, and alkyl-sulfonic acid groups, respectively. All ionomers were synthesized and characterized by 1H and 19F NMR. A novel ionomer synthesized with a pendant perfluorinated sulfonic acid group and a poly(ether ether ketone) backbone showed the highest proton conductivity and proton diffusion coefficient among the three ionomers, demonstrating the effect of the perfluorinated side chains. The proton conductivity of the novel ionomer was comparable to that of Nafion over a wide humidity range and temperature. A lithium perfluorosulfonate ionomer based on aromatic poly(arylene ether)s with pendant lithium perfluoroethyl sulfonates was prepared by ion exchange of the perlfuorosulfonic acid ionomer, and subsequently incoroporated into a lithium-ion battery cell as a single-ion conducting electrolyte. The microporous polymer film saturated with organic carbonates exhibited a nearly unity Li + transfer number, high ionic conductivity (e.g. > 10-3 S m-1 at room temperature) over a wide range of temperatures, high electrochemical stability, and excellent mechanical properties. Excellent cyclability with almost identical charge and discharge capacities have been demonstrated at ambient temperature in the batteries assembled from the prepared single-ion conductors. The mechanical stability of the polymer film was attributed to the rigid polymer backbone which was largely unaffected by the presence of plasticizing organic solvents, while the porous channels with high concentration of the perfluorinated side chains resulted in high ionic conductivity. The expected high charge-rate performance was not achieved, however, due to the high interfacial impedance present between the polymer electrolyte and the electrodes. Several procedural modifications were employed in order to decrease the interfacial impedance of the battery cell. The poly(arylene ether) based ionomer was saturated with an ionic liquid mixture, in order to explore the possibility of its application as a safe, inflammable electrolyte. A low-viscosity ionic liquid with high ionic conductivity, 1-butyl-3-methylimidazolium thiocyanate which has never been successfully utilized as an electrolyte for lithium-ion batteries was incorporated into a battery cell as a solvent mixture with propylene carbonate and lithium bis(trifluoromethane)sulfonimide impregnated in a free-standing hybrid electrolyte film. Outstanding ionic conductivity was achieved and the lithium half cell comprising a LTO cathode and a lithium metal anode separated by the solid polymer electrolyte showed good cyclability at room temperature and even at 0°C. The presence of a sufficient amount of propylene carbonate, which resulted in flammability of the polymer electrolyte, was discovered to be critical in the electrochemical stability of the polymer electrolyte.
Plastic microfibre ingestion by deep-sea organisms
NASA Astrophysics Data System (ADS)
Taylor, M. L.; Gwinnett, C.; Robinson, L. F.; Woodall, L. C.
2016-09-01
Plastic waste is a distinctive indicator of the world-wide impact of anthropogenic activities. Both macro- and micro-plastics are found in the ocean, but as yet little is known about their ultimate fate and their impact on marine ecosystems. In this study we present the first evidence that microplastics are already becoming integrated into deep-water organisms. By examining organisms that live on the deep-sea floor we show that plastic microfibres are ingested and internalised by members of at least three major phyla with different feeding mechanisms. These results demonstrate that, despite its remote location, the deep sea and its fragile habitats are already being exposed to human waste to the extent that diverse organisms are ingesting microplastics.
Magi Meconi, Giulia; Ballard, Nicholas; Asua, José M; Zangi, Ronen
2017-12-06
Although surfactants are known to play a vital role in polymerization reactions carried out in dispersed media, many aspects of their use are poorly understood, perhaps none more so than the vastly different action of ionic and nonionic surfactants in emulsion polymerization. In this work, we combine experimental measurements of emulsion polymerization of styrene with atomistic molecular dynamics simulations to better understand the behavior of surfactants at monomer/polymer-water interfaces. In a batch emulsion polymerization of styrene, the nonionic surfactant Disponil AFX 1080 leads to two nucleation periods, in contrast to the behavior observed for the ionic surfactant SDS. This can be explained by the absorption of the nonionic surfactant into the organic phase at the early stages of the polymerization reaction which is then released as the reaction progresses. Indeed, we find that the partition coefficient of the surfactant between the organic phase and water increases with the amount of monomer in the former, and preferential partitioning is detected to organic phases containing at least 55% styrene. Results from molecular dynamics simulations confirm that spontaneous dissolution of the non-ionic surfactant into a styrene-rich organic phase occurs above a critical concentration of the surfactant adsorbed at the interface. Above this critical concentration, a linear correlation between the amount of surfactant adsorbed at the interface and that absorbed inside the organic phase is observed. To facilitate this absorption into a completely hydrophobic medium, water molecules accompany the intruding surfactants. Similar simulations but with the ionic surfactant instead did not result in any absorption of the surfactant into a neat styrene phase, likely because of its strongly hydrophilic head group. The unusual partitioning behavior of nonionic surfactants explains a number of observable features of emulsion polymerization reactions which use nonionic surfactants and should help with future development of processes for improved control over polymerization.
Federal Register 2010, 2011, 2012, 2013, 2014
2011-01-27
... Promulgation of Air Quality Implementation Plans; Ohio; Volatile Organic Compound Reinforced Plastics...) emissions from reinforced plastic composites production operations to Ohio's State Implementation plan (SIP). This rule applies to any facility that has reinforced plastic composites production operations. This...
Tsuchida, Daisuke; Kajihara, Yusuke; Shimidzu, Nobuhiro; Hamamura, Kengo; Nagase, Makoto
2011-06-01
In the present study it was demonstrated that organic additives eluted from plastic resins could be utilized as substrates by sulfate-reducing bacteria. Two laboratory-scale experiments, a microcosm experiment and a leaching experiment, were conducted using polyvinyl chloride (PVC) as a model plastic resin. In the former experiment, the conversion of sulfate to sulfide was evident in microcosms that received plasticized PVC as the sole carbon source, but not in those that received PVC homopolymer. Additionally, dissolved organic carbon accumulated only in microcosms that received plasticized PVC, indicating that the dissolved organic carbon originated from additives. In the leaching experiment, phenol and bisphenol A were found in the leached solutions. These results suggest that the disposal of waste plastics in inert waste landfills may result in the production of H(2)S.
Superbase-derived protic ionic liquid extractants for metal ion separation
DOE Office of Scientific and Technical Information (OSTI.GOV)
Bell, Jason R.; Dai, Sheng; Luo, Huimin
2014-04-19
Solvent extraction of La 3+ and Ba 2+ by an ionic liquid extractant in an imidazolium-based ionic liquid diluent was investigated. Seven protic ionic liquid extractants were examined and these protic ILs are based on five organic superbases and either 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octadione (Hfod) or 1,1,1,5,5,5-hexafluoroacetylacetone (Hhfac) -diketones as anion. For fod-based extractants, the extraction efficiencies and separation factors were found to be concentration dependent. The effects of aqueous phase acidity, extractant structure, and extractant concentration on separation properties of La 3+ and Ba 2+ are discussed in this paper.
Phenotypic plasticity with instantaneous but delayed switches.
Utz, Margarete; Jeschke, Jonathan M; Loeschcke, Volker; Gabriel, Wilfried
2014-01-07
Phenotypic plasticity is a widespread phenomenon, allowing organisms to better adapt to changing environments. Most empirical and theoretical studies are restricted to irreversible plasticity where the expression of a specific phenotype is mostly determined during development. However, reversible plasticity is not uncommon; here, organisms are able to switch back and forth between phenotypes. We present two optimization models for the fitness of (i) non-plastic, (ii) irreversibly plastic, and (iii) reversibly plastic genotypes in a fluctuating environment. In one model, the fitness values of an organism during different life phases act together multiplicatively (so as to consider traits that are related to survival). The other model additionally considers additive effects (corresponding to traits related to fecundity). Both models yield qualitatively similar results. If the only costs of reversible plasticity are due to temporal maladaptation while switching between phenotypes, reversibility is virtually always advantageous over irreversibility, especially for slow environmental fluctuations. If reversibility implies an overall decreased fitness, then irreversibility is advantageous if the environment fluctuates quickly or if stress events last relatively short. Our results are supported by observations from different types of organisms and have implications for many basic and applied research questions, e.g., on invasive alien species. © 2013 Elsevier Ltd. Published by Elsevier Ltd. All rights reserved.
Novel, Solvent-Free, Single Ion-Conductive Polymer Electrolytes
2008-02-01
tetrahedron structure wherein no hydrogen is present. The main advantage of the use of LiBOB salt is the high ionic conductivity at low-ambient...In addition to its plasticizing effect, the LiBOB salt offers other important advantages such as: no risk of production of harmful gases and/or...6 to the (120) reflection. Increase of CP concentration up to 1:0.5 salt -to-additive ratio in the SiO2-containing PE is followed by a
Polymorphic phase transitions and molecular motion in pyridinium chlorochromate
NASA Astrophysics Data System (ADS)
Pajaķ, Z.; Szafrańska, B.; Czarnecki, P.; Mayer, J.; Kozak, A.
1997-08-01
DTA, DSC, NMR and dielectric studies have been performed for pyridinium chlorochromate over a wide temperature range. A sequence of four solid-solid phase transitions was discovered. The in-plane complex reorientation of the cation is described by a three-well potential model with two correlation times. At higher temperatures one observes simultaneous cation tumbling and diffusion. Thus existence of a new ionic plastic phase is revealed. The domain structure observed suggests ferroelastic properties of the compound.
Photoconversion of gasified organic materials into biologically-degradable plastics
Weaver, P.F.; Pinching Maness.
1993-10-05
A process is described for converting organic materials (such as biomass wastes) into a bioplastic suitable for use as a biodegradable plastic. In a preferred embodiment the process involves thermally gasifying the organic material into primarily carbon monoxide and hydrogen, followed by photosynthetic bacterial assimilation of the gases into cell material. The process is ideally suited for waste recycling and for production of useful biodegradable plastic polymer. 3 figures.
Photoconversion of gasified organic materials into biologically-degradable plastics
Weaver, Paul F.; Maness, Pin-Ching
1993-01-01
A process is described for converting organic materials (such as biomass wastes) into a bioplastic suitable for use as a biodegradable plastic. In a preferred embodiment the process involves thermally gasifying the organic material into primarily carbon monoxide and hydrogen, followed by photosynthetic bacterial assimilation of the gases into cell material. The process is ideally suited for waste recycling and for production of useful biodegradable plastic polymer.
Parthier, Daniel; Frings, Stephan; Möhrlen, Frank
2015-01-01
Calcium-activated chloride channels of the anoctamin (alias TMEM16) protein family fulfill critical functions in epithelial fluid transport, smooth muscle contraction and sensory signal processing. Little is known, however, about their contribution to information processing in the central nervous system. Here we examined the recent finding that a calcium-dependent chloride conductance impacts on GABAergic synaptic inhibition in Purkinje cells of the cerebellum. We asked whether anoctamin channels may underlie this chloride conductance. We identified two anoctamin channel proteins, ANO1 and ANO2, in the cerebellar cortex. ANO1 was expressed in inhibitory interneurons of the molecular layer and the granule cell layer. Both channels were expressed in Purkinje cells but, while ANO1 appeared to be retained in the cell body, ANO2 was targeted to the dendritic tree. Functional studies confirmed that ANO2 was involved in a calcium-dependent mode of ionic plasticity that reduces the efficacy of GABAergic synapses. ANO2 channels attenuated GABAergic transmission by increasing the postsynaptic chloride concentration, hence reducing the driving force for chloride influx. Our data suggest that ANO2 channels are involved in a Ca2+-dependent regulation of synaptic weight in GABAergic inhibition. Thus, in balance with the chloride extrusion mechanism via the co-transporter KCC2, ANO2 appears to regulate ionic plasticity in the cerebellum. PMID:26558388
Frequency-dependent learning achieved using semiconducting polymer/electrolyte composite cells
NASA Astrophysics Data System (ADS)
Dong, W. S.; Zeng, F.; Lu, S. H.; Liu, A.; Li, X. J.; Pan, F.
2015-10-01
Frequency-dependent learning has been achieved using semiconducting polymer/electrolyte composite cells. The cells composed of polymer/electrolyte double layers realized the conventional spike-rate-dependent plasticity (SRDP) learning model. These cells responded to depression upon low-frequency stimulation and to potentiation upon high-frequency stimulation and presented long-term memory. The transition threshold θm from depression to potentiation varied depending on the previous stimulations. A nanostructure resembling a bio-synapse in its transport passages was demonstrated and a random channel model was proposed to describe the ionic kinetics at the polymer/electrolyte interface during and after stimulations with various frequencies, accounting for the observed SRDP.Frequency-dependent learning has been achieved using semiconducting polymer/electrolyte composite cells. The cells composed of polymer/electrolyte double layers realized the conventional spike-rate-dependent plasticity (SRDP) learning model. These cells responded to depression upon low-frequency stimulation and to potentiation upon high-frequency stimulation and presented long-term memory. The transition threshold θm from depression to potentiation varied depending on the previous stimulations. A nanostructure resembling a bio-synapse in its transport passages was demonstrated and a random channel model was proposed to describe the ionic kinetics at the polymer/electrolyte interface during and after stimulations with various frequencies, accounting for the observed SRDP. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr02891d
Clewett, G.H.; Lee, DeW.A.
1958-05-20
A new method is described for isotopic enrichment of uranium. It has been found that when an aqueous acidic solution of ionic tetravalent uraniunn is contacted with chelate complexed tetravalent uranium, the U/sup 238/ preferentially concentrates in the complexed phase while U/sup 235/ concentrates in the ionic phase. The effect is enhanced when the chelate compound is water insoluble and is dissolved in a water-immiscible organic solvent. Cupferron is one of a number of sultable complexing agents, and chloroform is a suitable organic solvent.
Pyrene-Tagged Ionic Liquids: Separable Organic Catalysts for SN2 Fluorination.
Taher, Abu; Lee, Kyo Chul; Han, Hye Ji; Kim, Dong Wook
2017-07-07
We prepared pyrene-substituted imidazolium-based ionic liquids (PILs) as organic catalysts for the S N 2 fluorination using alkali metal fluoride (MF). In this system, the PIL significantly enhanced the reactivity of MF due to the phase-transfer catalytic effect of the imidazolium moiety as well as the metal cation-π (pyrene) interactions. Furthermore, this homogeneous catalyst PIL was easily separated from the reaction mixture using reduced graphene oxide by π-π stacking with the pyrene of PIL.
Larangeira, Paula Martins; de Rosso, Veridiana Vera; da Silva, Victor Hugo Pereira; de Moura, Carolina Foot Gomes; Ribeiro, Daniel Araki
2016-11-01
The ionic liquid or melted salt 1-Butyl-3-methylimidazolium is an alternative process to extract natural pigments, such as carotenoids. Lycopene represents 80-90% of total of carotenoids presents in tomatoes and it has been widely studied due its potent antioxidant action. The aim of this study was to evaluate genotoxicity, mutagenicity and cytotoxicity of carotenoids extracted from ionic liquid using experimental model in vivo. For this purpose, a total of 20 male Wistar rats were distributed into four groups (n=5), as follows: control group; received a corresponding amount of corn oil for 7days by intragastric gavage (i.g.), ionic liquid group, received 10mgkg -1 body weight for 7days by gavage; 10mg carotenoids group, received 10mgkg -1 bw dissolved in corn oil for 7days by gavage and 500mg carotenoids group, received 500mgkg -1 bw dissolved in corn oil for 7days by gavage. Rat liver treated with ionic liquid exhibited moderate histopathological changes randomly distributed in the parenchyma, such as cytoplasmic eosinophilia, apoptotic bodies, inflammatory infiltrate and focal necrosis. DNA damage was found in peripheral blood and liver cells of rats treated with ionic liquid or carotenoids at 500mg. An increase of micronucleated cells and 8-OhDG immunopositive cells were also detected in rats treated with carotenoids at 500mg. In summary, our results demonstrate that recommended dose for human daily intake of carotenoids extracted by ionic liquid did not induce genotoxicity, mutagenicity and cytotoxicity in multiple organs of rats. Copyright © 2016 Elsevier GmbH. All rights reserved.
NASA Astrophysics Data System (ADS)
Sreeram, Arvind
Conjugated polymers have found several applications in recent years, in energy conversion and storage devices such as organic light emitting diodes, solar cells, batteries, and super capacitors. Thin films of polymers used for these applications need to be mechanically and thermally stable to withstand the harsh operating conditions. Although there is significant information on the optoelectronic properties of many of these polymers, there are only few studies on their mechanical properties. There is little information in the literature on how processing of these films influence mechanical properties. In the first part of this study, poly(p-phenylene vinylene) (PPV) films were prepared by thermolytic conversion of poly[p -phenylene (tetrahydrothiophenium)ethylene chloride] precursor films, at different temperatures and the kinetics of reaction was investigated using thermogravimetry and Fourier transform infrared (FTIR) spectroscopy. The mechanical properties of the films, studied using nanoindentation, showed a dependence on the extent of conversion and chemical composition of the films. The presence of chemical defects (e.g., carbonyl groups, detected using FTIR spectroscopy), was also found to have a noticeable effect on the modulus and hardness of the films. The storage modulus, E', and plasticity decreased with an increase in conversion, whereas the loss modulus, E", showed the opposite trend. Both the precursor and the fully-converted PPV films were found to have significantly lower E" than E', consistent with the glassy nature of the polymers at room temperature. In the second part of the study, polyacetylene films were synthesized by acid-catalyzed dehydration reaction of poly(vinyl alcohol) (PVA) precursor films. The kinetics of this reaction was monitored by thermogravimetry. The chemical structure of the conjugated polymer films was characterized by Raman and IR spectroscopy. Polyacetylene films incorporated with 1-propyl-3-methylimidazolium ionic liquid (IL) could be obtained in a single step reaction. The incorporation of IL in the film, not only greatly improved its mechanical properties, by acting as a plasticizer, but also imparted a dual mechanism of charge transport. The segments of conjugated double bonds imparted electronic conductivity to the films, and the IL resulted in ionic conductivity. The presence of both electronic and ionic conduction pathways in the films was confirmed by electrochemical impedance spectroscopy (EIS). These IL-imbibed conjugated polymer films are promising as materials for electrochemical energy conversion and storage. In the third part of this work, conjugated polymer films containing multiwalled carbon nanotubes (MWNT) and graphene nanoplatelets (GNP) were synthesized and characterized. PPV--MWNT nanocomposite films and PA--GNP nanocomposite films were characterized using a variety of analytical techniques including transmission electron microscopy, quasistatic and dynamic nanoindentaiton, electrochemical impedance spectroscopy, and cyclic voltammetry. Potential application of these films is in electrochemical supercapacitors.
Federal Register 2010, 2011, 2012, 2013, 2014
2011-07-13
... Promulgation of Air Quality Implementation Plans; Ohio; Volatile Organic Compound Reinforced Plastic Composites... compound (VOC) emissions from reinforced plastic composites production operations. This rule applies to any facility that has reinforced plastic composites production operations. This rule is approvable because it...
Hodgson, D J; Bréchon, A L; Thompson, R C
2018-02-01
Inappropriate disposal of plastic debris has led to the contamination of marine habitats worldwide. This debris can be ingested by organisms; however, the extent to which chewing and gut transit modifies plastic debris is unclear. Detritivores, such as amphipods, ingest and shred natural organic matter and are fundamental to its breakdown. Here we examine ingestion and shredding of plastic carrier bags by Orchestia gammarellus. A laboratory experiment showed these amphipods shredded plastic carrier bags, generating numerous microplastic fragments (average diameter 488.59μm). The presence of a biofilm significantly increased the amount of shredding, but plastic type (conventional, degradable and biodegradable) had no effect. Subsequent field observations confirmed similar shredding occurred on the strandline. Rates of shredding will vary according to amphipod density; however, our data indicates that shredding by organisms could substantially accelerate the formation microplastics in the environment. Crown Copyright © 2017. Published by Elsevier Ltd. All rights reserved.
Facile and scalable fabrication of polymer-ceramic composite electrolyte with high ceramic loadings
DOE Office of Scientific and Technical Information (OSTI.GOV)
Pandian, Amaresh Samuthira; Chen, Xi Chelsea; Chen, Jihua
Solid state electrolytes are a promising alternative to flammable liquid electrolytes for high-energy lithium battery applications. In this work polymer-ceramic composite electrolyte membrane with high ceramic loading (greater than 60 vol%) is fabricated using a model polymer electrolyte poly(ethylene oxide) + lithium trifluoromethane sulfonate and a lithium-conducting ceramic powder. The effects of processing methods, choice of plasticizer and varying composition on ionic conductivity of the composite electrolyte are thoroughly investigated. The physical, structural and thermal properties of the composites are exhaustively characterized. We demonstrate that aqueous spray coating followed by hot pressing is a scalable and inexpensive technique to obtainmore » composite membranes that are amazingly dense and uniform. The ionic conductivity of composites fabricated using this protocol is at least one order of magnitude higher than those made by dry milling and solution casting. The introduction of tetraethylene glycol dimethyl ether further increases the ionic conductivity. The composite electrolyte's interfacial compatibility with metallic lithium and good cyclability is verified by constructing lithium symmetrical cells. As a result, a remarkable Li + transference number of 0.79 is discovered for the composite electrolyte.« less
Facile and scalable fabrication of polymer-ceramic composite electrolyte with high ceramic loadings
Pandian, Amaresh Samuthira; Chen, Xi Chelsea; Chen, Jihua; ...
2018-04-24
Solid state electrolytes are a promising alternative to flammable liquid electrolytes for high-energy lithium battery applications. In this work polymer-ceramic composite electrolyte membrane with high ceramic loading (greater than 60 vol%) is fabricated using a model polymer electrolyte poly(ethylene oxide) + lithium trifluoromethane sulfonate and a lithium-conducting ceramic powder. The effects of processing methods, choice of plasticizer and varying composition on ionic conductivity of the composite electrolyte are thoroughly investigated. The physical, structural and thermal properties of the composites are exhaustively characterized. We demonstrate that aqueous spray coating followed by hot pressing is a scalable and inexpensive technique to obtainmore » composite membranes that are amazingly dense and uniform. The ionic conductivity of composites fabricated using this protocol is at least one order of magnitude higher than those made by dry milling and solution casting. The introduction of tetraethylene glycol dimethyl ether further increases the ionic conductivity. The composite electrolyte's interfacial compatibility with metallic lithium and good cyclability is verified by constructing lithium symmetrical cells. As a result, a remarkable Li + transference number of 0.79 is discovered for the composite electrolyte.« less
Chen, Yuehua; Wang, Huiyong; Wang, Jianji
2014-05-01
Thermodynamic dissociation constants of the Brønsted acidic ionic liquids (ILs) are important for their catalytic and separation applications. In this work, a series of imidazolium bromides with one carboxylic acid substitute group in their alkyl chain ([{(CH2)nCOOH}mim]Br, n = 1,3,5,7) have been synthesized, and their dissociation constants (pKa) at different ionic strengths have been determined in aqueous and aqueous organic solvents at 0.1 mole fraction (x) of ethanol, glycol, iso-propanol, and dimethyl sulfoxide by potentiometric titrations at 298.2 K. The standard thermodynamic dissociation constants (pKa(T)) of the ILs in these solvents were calculated from the extended Debye-Hückel equation. It was found that the pKa values increased with the increase of ionic strength of the media and of the addition of organic solvent in water. The pKa(T) values also increased with the increase of the alkyl chain length of cations of the ILs. In addition, the effect of solvent nature on pKa(T) values is interpreted from solvation of the dissociation components and their Gibbs energy of transfer from water to aqueous organic solutions.
Synaptic plasticity functions in an organic electrochemical transistor
NASA Astrophysics Data System (ADS)
Gkoupidenis, Paschalis; Schaefer, Nathan; Strakosas, Xenofon; Fairfield, Jessamyn A.; Malliaras, George G.
2015-12-01
Synaptic plasticity functions play a crucial role in the transmission of neural signals in the brain. Short-term plasticity is required for the transmission, encoding, and filtering of the neural signal, whereas long-term plasticity establishes more permanent changes in neural microcircuitry and thus underlies memory and learning. The realization of bioinspired circuits that can actually mimic signal processing in the brain demands the reproduction of both short- and long-term aspects of synaptic plasticity in a single device. Here, we demonstrate the implementation of neuromorphic functions similar to biological memory, such as short- to long-term memory transition, in non-volatile organic electrochemical transistors (OECTs). Depending on the training of the OECT, the device displays either short- or long-term plasticity, therefore, exhibiting non von Neumann characteristics with merged processing and storing functionalities. These results are a first step towards the implementation of organic-based neuromorphic circuits.
Cecchini, Martina Maya; Charnay, Clarence; De Angelis, Francesco; Lamaty, Frédéric; Martinez, Jean; Colacino, Evelina
2014-01-01
PEG-based ionic liquids are a new appealing group of solvents making the link between two distinct but very similar fluids: ionic liquids and poly(ethylene glycol)s. They find applications across a range of innumerable disciplines in science, technology, and engineering. In the last years, the possibility to use these as alternative solvents for organic synthesis and catalysis has been increasingly explored. This Review highlights strategies for their synthesis, their physical properties (critical point, glass transition temperature, density, rheological properties), and their application in reactions catalyzed by metals (such as Pd, Cu, W, or Rh) or as organic solvent (for example for multicomponent reactions, organocatalysis, CO2 transformation) with special emphasis on their toxicity, environmental impact, and biodegradability. These aspects, very often neglected, need to be considered in addition to the green criteria usually considered to establish ecofriendly processes. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Plastic microfibre ingestion by deep-sea organisms
Taylor, M. L.; Gwinnett, C.; Robinson, L. F.; Woodall, L. C.
2016-01-01
Plastic waste is a distinctive indicator of the world-wide impact of anthropogenic activities. Both macro- and micro-plastics are found in the ocean, but as yet little is known about their ultimate fate and their impact on marine ecosystems. In this study we present the first evidence that microplastics are already becoming integrated into deep-water organisms. By examining organisms that live on the deep-sea floor we show that plastic microfibres are ingested and internalised by members of at least three major phyla with different feeding mechanisms. These results demonstrate that, despite its remote location, the deep sea and its fragile habitats are already being exposed to human waste to the extent that diverse organisms are ingesting microplastics. PMID:27687574
Structural and electrochemical properties of PEMA with the influence of MWCNT / TiO{sub 2} filler
DOE Office of Scientific and Technical Information (OSTI.GOV)
Pradeepa, P.; Raj, S. Edwin; Kalaiselvimary, J.
An attempt has been made to prepare a hybrid Nano composite polymer electrolytes (NCPES) based on Poly(ethyl methacrylate) (PEMA) doped with multiwalled carbon nanotubes (MWCNT) and Titanium oxide (TiO{sub 2}) as additives, Lithium per chlorate (LiClO{sub 4}) as ionic salt and Propylene Carbonate as plasticizer (PC) by using solvent casting technique. X-ray diffraction analysis (XRD) confirms the miscibility and amorphous nature of the prepared electrolytes. It has been found from the a.c impedance analysis that the inorganic filler reduces the bulk resistance of the electrolytes and thus ionic conductivity enhanced. A high dielectric loss value is observed for the casemore » of doped MWCNT-PEMA in comparison with pure PEMA and doped TiO{sub 2} –PEMA membranes. Based on the study of relaxation spectra, it is found that the relaxation time decreases with increase in temperature.« less
Landauer, Alexander K.; Barnhill, William C.; Qu, Jun
2016-03-10
Here we examine the elasticity, hardness, and resistance-to-plastic-deformation (P/S 2) measured via nanoindentation of several tribofilms and correlates these properties to friction and wear behavior. The tribofilms were generated by ball-on-plate reciprocating sliding lubricated by a base oil containing an ionic liquid, phosphonium-organophosphate or ammonium-organophosphate, zinc dialkyldithiophosphate (ZDDP), or combination of IL and ZDDP. Nanoindentation was conducted at room and elevated temperatures. While there seems little correlation between the tribofilm hardness and tribological behavior, a higher modulus generally leads to better friction and wear performance. Interestingly, a lower P/S 2 ratio tends to reduce friction and improve wear protection, whichmore » is in an opposite trend as reported for bulk materials. Ultimately, this is likely attributable to the dynamic, self-healing characteristics of tribofilms.« less
A resonant force sensor based on ionic polymer metal composites
NASA Astrophysics Data System (ADS)
Bonomo, Claudia; Fortuna, Luigi; Giannone, Pietro; Graziani, Salvatore; Strazzeri, Salvatore
2008-02-01
In this paper a novel force sensor, based on ionic polymer metal composites (IPMCs), is presented. The system has DC sensing capabilities and is able to work in the range of a few millinewtons. IPMCs are emerging materials used to realize motion actuators and sensors. An IPMC strip is activated in a beam fixed/simply-supported configuration. The beam is tightened at the simply-supported end by a force. This influences the natural resonant frequency of the beam; the value of the resonant frequency is used in the proposed system to estimate the force applied in the axial direction. The performance of the system based on the IPMC material has proved to be comparable with that of sensors based on other sensing mechanisms. This suggests the possibility of using this class of polymeric devices to realize PMEMS (plastic micro electrical mechanical systems) sensors.
Potential transfer of organic pollutants from littoral plastics debris to the marine environment.
León, Víctor M; García, Inés; González, Emilia; Samper, Raquel; Fernández-González, Verónica; Muniategui-Lorenzo, Soledad
2018-05-01
Plastic polymers act as passive samplers in air system and concentrate hydrophobic organic contaminants by sorption or specific interactions, which can be transported to other systems such as the marine environment. In this study plastic debris was sampled in the surrounding area of a Mediterranean lagoon in order to determine the concentration of persistent and emerging organic contaminants. More specifically, desorption of 91 regulated and emerging organic contaminants (polycyclic aromatic hydrocarbons, polychlorinated biphenyls, organochlorinated pesticides, current-use pesticides, personal care products, other pesticides and plastic additives) was characterized for the first 24 h from different polymers to seawater and the remaining content of these contaminants was also extracted by ultrasonic extraction with methanol. All samples were analyzed by Stir Bar Sorptive Extraction coupled to GC/MS. A significant fraction of sorbed contaminants in polymers was desorbed in the first 24 h, particularly for triazines and organophosphorus pesticides due to their lower hydrophobicity than other considered analytes. The remaining contaminants contained in plastics can be also transferred to seawater, sediments or biota. Considering 24 h desorbed fraction plus the remaining methanol extracted fraction, the highest transfer levels corresponded to personal care products, plastic additives, current-use pesticides and PAHs. This is the first study to show the relevance of the transport of organic contaminants on plastic debris from littoral areas to the marine environment. Copyright © 2018 Elsevier Ltd. All rights reserved.
Contrasting Acute and Slow-Growing Lesions: A New Door to Brain Plasticity
ERIC Educational Resources Information Center
Desmurget, Michel; Bonnetblanc, FranCois; Duffau, Hugues
2007-01-01
The concept of plasticity describes the mechanisms that rearrange cerebral organization following a brain injury. During the last century, plasticity has been mainly investigated in humans with acute strokes. It was then shown: (i) that the brain is organized into highly specialized functional areas, often designated "eloquent" areas and (ii) that…
Does titanium in ionic form display a tissue-specific distribution?
Golasik, Magdalena; Wrobel, Pawel; Olbert, Magdalena; Nowak, Barbara; Czyzycki, Mateusz; Librowski, Tadeusz; Lankosz, Marek; Piekoszewski, Wojciech
2016-06-01
Most studies have focused on the biodistribution of titanium(IV) oxide as nanoparticles or crystals in organism. But several reports suggested that titanium is released from implant in ionic form. Therefore, gaining insight into toxicokinetics of Ti ions will give valuable information, which may be useful when assessing the health risks of long-term exposure to titanium alloy implants in patients. A micro synchrotron radiation-induced X-ray fluorescence (µ-SRXRF) was utilized to investigate the titanium distribution in the liver, spleen and kidneys of rats following single intravenous or 30-days oral administration of metal (6 mg Ti/b.w.) in ionic form. Titanium was mainly retained in kidneys after both intravenous and oral dosing, and also its compartmentalization in this organ was observed. Titanium in the liver was non-uniformly distributed-metal accumulated in single aggregates, and some of them were also enriched in calcium. Correlation analysis showed that metal did not displace essential elements, and in liver titanium strongly correlated with calcium. Two-dimensional maps of Ti distribution show that the location of the element is characteristic for the route of administration and time of exposure. We demonstrated that µ-SRXRF can provide information on the distribution of titanium in internal structures of whole organs, which helps in enhancing our understanding of the mechanism of ionic titanium accumulation in the body. This is significant due to the popularity of titanium implants and the potential release of metal ions from them to the organism.
Lian, Cheng; Univ. of California, Riverside, CA; Liu, Honglai; ...
2016-08-22
The ionophobicity effect of nanoporous electrodes on the capacitance and the energy storage capacity of nonaqueous-electrolyte supercapacitors is studied by means of the classical density functional theory (DFT). It has been hypothesized that ionophobic nanopores may create obstacles in charging, but they store energy much more efficiently than ionophilic pores. In this paper, we find that, for both ionic liquids and organic electrolytes, an ionophobic pore exhibits a charging behavior different from that of an ionophilic pore, and that the capacitance–voltage curve changes from a bell shape to a two-hump camel shape when the pore ionophobicity increases. For electric-double-layer capacitorsmore » containing organic electrolytes, an increase in the ionophobicity of the nanopores leads to a higher capacity for energy storage. Without taking into account the effects of background screening, the DFT predicts that an ionophobic pore containing an ionic liquid does not enhance the supercapacitor performance within the practical voltage ranges. However, by using an effective dielectric constant to account for ion polarizability, the DFT predicts that, like an organic electrolyte, an ionophobic pore with an ionic liquid is also able to increase the energy stored when the electrode voltage is beyond a certain value. We find that the critical voltage for an enhanced capacitance in an ionic liquid is larger than that in an organic electrolyte. Finally, our theoretical predictions provide further understanding of how chemical modification of porous electrodes affects the performance of supercapacitors.« less
Transport and release of chemicals from plastics to the environment and to wildlife.
Teuten, Emma L; Saquing, Jovita M; Knappe, Detlef R U; Barlaz, Morton A; Jonsson, Susanne; Björn, Annika; Rowland, Steven J; Thompson, Richard C; Galloway, Tamara S; Yamashita, Rei; Ochi, Daisuke; Watanuki, Yutaka; Moore, Charles; Viet, Pham Hung; Tana, Touch Seang; Prudente, Maricar; Boonyatumanond, Ruchaya; Zakaria, Mohamad P; Akkhavong, Kongsap; Ogata, Yuko; Hirai, Hisashi; Iwasa, Satoru; Mizukawa, Kaoruko; Hagino, Yuki; Imamura, Ayako; Saha, Mahua; Takada, Hideshige
2009-07-27
Plastics debris in the marine environment, including resin pellets, fragments and microscopic plastic fragments, contain organic contaminants, including polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons, petroleum hydrocarbons, organochlorine pesticides (2,2'-bis(p-chlorophenyl)-1,1,1-trichloroethane, hexachlorinated hexanes), polybrominated diphenylethers, alkylphenols and bisphenol A, at concentrations from sub ng g(-1) to microg g(-1). Some of these compounds are added during plastics manufacture, while others adsorb from the surrounding seawater. Concentrations of hydrophobic contaminants adsorbed on plastics showed distinct spatial variations reflecting global pollution patterns. Model calculations and experimental observations consistently show that polyethylene accumulates more organic contaminants than other plastics such as polypropylene and polyvinyl chloride. Both a mathematical model using equilibrium partitioning and experimental data have demonstrated the transfer of contaminants from plastic to organisms. A feeding experiment indicated that PCBs could transfer from contaminated plastics to streaked shearwater chicks. Plasticizers, other plastics additives and constitutional monomers also present potential threats in terrestrial environments because they can leach from waste disposal sites into groundwater and/or surface waters. Leaching and degradation of plasticizers and polymers are complex phenomena dependent on environmental conditions in the landfill and the chemical properties of each additive. Bisphenol A concentrations in leachates from municipal waste disposal sites in tropical Asia ranged from sub microg l(-1) to mg l(-1) and were correlated with the level of economic development.
Transport and release of chemicals from plastics to the environment and to wildlife
Teuten, Emma L.; Saquing, Jovita M.; Knappe, Detlef R. U.; Barlaz, Morton A.; Jonsson, Susanne; Björn, Annika; Rowland, Steven J.; Thompson, Richard C.; Galloway, Tamara S.; Yamashita, Rei; Ochi, Daisuke; Watanuki, Yutaka; Moore, Charles; Viet, Pham Hung; Tana, Touch Seang; Prudente, Maricar; Boonyatumanond, Ruchaya; Zakaria, Mohamad P.; Akkhavong, Kongsap; Ogata, Yuko; Hirai, Hisashi; Iwasa, Satoru; Mizukawa, Kaoruko; Hagino, Yuki; Imamura, Ayako; Saha, Mahua; Takada, Hideshige
2009-01-01
Plastics debris in the marine environment, including resin pellets, fragments and microscopic plastic fragments, contain organic contaminants, including polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons, petroleum hydrocarbons, organochlorine pesticides (2,2′-bis(p-chlorophenyl)-1,1,1-trichloroethane, hexachlorinated hexanes), polybrominated diphenylethers, alkylphenols and bisphenol A, at concentrations from sub ng g–1 to µg g–1. Some of these compounds are added during plastics manufacture, while others adsorb from the surrounding seawater. Concentrations of hydrophobic contaminants adsorbed on plastics showed distinct spatial variations reflecting global pollution patterns. Model calculations and experimental observations consistently show that polyethylene accumulates more organic contaminants than other plastics such as polypropylene and polyvinyl chloride. Both a mathematical model using equilibrium partitioning and experimental data have demonstrated the transfer of contaminants from plastic to organisms. A feeding experiment indicated that PCBs could transfer from contaminated plastics to streaked shearwater chicks. Plasticizers, other plastics additives and constitutional monomers also present potential threats in terrestrial environments because they can leach from waste disposal sites into groundwater and/or surface waters. Leaching and degradation of plasticizers and polymers are complex phenomena dependent on environmental conditions in the landfill and the chemical properties of each additive. Bisphenol A concentrations in leachates from municipal waste disposal sites in tropical Asia ranged from sub µg l–1 to mg l–1 and were correlated with the level of economic development. PMID:19528054
NASA Astrophysics Data System (ADS)
Aihara, Yuichi; Sugimoto, Kyoko; Price, William S.; Hayamizu, Kikuko
2000-08-01
The Debye-Hückel-Onsager and Nernst-Einstein equations, which are based on two different conceptual approaches, constitute the most widely used equations for relating ionic conduction to ionic mobility. However, both of these classical (simple) equations are predictive of ionic conductivity only at very low salt concentrations. In the present work the ionic conductivity of four organic solvent-lithium salt-based electrolytes were measured. These experimental conductivity values were then contrasted with theoretical values calculated using the translational diffusion (also known as self-diffusion or intradiffusion) coefficients of all of the species present obtained using pulsed-gradient spin-echo (1H, 19F and 7Li) nuclear magnetic resonance self-diffusion measurements. The experimental results verified the applicability of both theoretical approaches at very low salt concentrations for these particular systems as well as helping to clarify the reasons for the divergence between theory and experiment. In particular, it was found that the correspondence between the Debye-Hückel-Onsager equation and experimental values could be improved by using the measured solvent self-diffusion values to correct for salt-induced changes in the solution viscosity. The concentration dependence of the self-diffusion coefficients is discussed in terms of the Jones-Dole equation.
Gonzalez García, Eric; Ressmann, Anna K; Gaertner, Peter; Zirbs, Ronald; Mach, Robert L; Krska, Rudolf; Bica, Katharina; Brunner, Kurt
2014-12-01
To date, the extraction of genomic DNA is considered a bottleneck in the process of genetically modified organisms (GMOs) detection. Conventional DNA isolation methods are associated with long extraction times and multiple pipetting and centrifugation steps, which makes the entire procedure not only tedious and complicated but also prone to sample cross-contamination. In recent times, ionic liquids have emerged as innovative solvents for biomass processing, due to their outstanding properties for dissolution of biomass and biopolymers. In this study, a novel, easily applicable, and time-efficient method for the direct extraction of genomic DNA from biomass based on aqueous-ionic liquid solutions was developed. The straightforward protocol relies on extraction of maize in a 10 % solution of ionic liquids in aqueous phosphate buffer for 5 min at room temperature, followed by a denaturation step at 95 °C for 10 min and a simple filtration to remove residual biopolymers. A set of 22 ionic liquids was tested in a buffer system and 1-ethyl-3-methylimidazolium dimethylphosphate, as well as the environmentally benign choline formate, were identified as ideal candidates. With this strategy, the quality of the genomic DNA extracted was significantly improved and the extraction protocol was notably simplified compared with a well-established method.
Plastic Scintillators for Pulse Shape Discrimination of Particle Types in Radiation Detection
NASA Astrophysics Data System (ADS)
Hajagos, Tibor Jacob
Organic scintillators have a long history in the field of radiation detection, dating back to some of the earliest studies of organic photophysics and optoelectronic properties. In particular, plastics have come to dominate the commercial market for organic scintillators, due to their low cost and ease of use and manufacturing, and more notably in spite of their poorer performance in many metrics. While there has been decades of active research since their inception, little progress has been made to improve upon the now well established compositions of commercial plastics, a notable exception being the recent development of plastic scintillators capable of pulse shape discrimination (PSD) of n/gamma radiation, which is of particular interest among governments and industry for the detection of illicit nuclear material and weapons. In recent years, much attention has been paid towards the study of luminescent organic materials, in particular due to the invention and widespread adoption of organic light emitting diode (OLED) based electronic devices, and the knowledge and lessons that have been fundamental to such fields have recently begun to be adopted by the organic scintilator community. In this work, new approaches to the design of both plastic scintillator components, and of the materials as a whole, are described, with particular emphasis paid towards the design and synthesis of small molecule scintillating dyes that are specifically tailored towards the development of PSD-capable plastic scintilators. In the first of these approaches, the design and synthesis of a highly soluble and polymerizable derivative of 9,10-diphenylanthracene is described, and the properties of plastic scintilators fabricated from this dye when copolymerized with poly(vinyl toluene) were investigated. This particular approach was used to demonstrate a proof-of-concept of PSD in highly loaded plastics stabilized through copolymerization of the primary dye, a strategy conceived to address the particular shortcomings of the current generation of PSD plastics. The second general approach investigated is the application of the phenomenon of thermally activated delayed fluorescence (TADF)--most notably a key innovation among the latest developments in OLED technologies--to the enhancement of the performance of organic sicntillators. Several key observations about the potential and efficacy of TADF dyes as novel organic scintillators were made, including a demonstration of the profound effects the TADF phenomenon can have on scintillation properties. These findings suggest that it is quite possible that TADF dyes could eventually enable an entirely new generation of high performance organic scintillators, and PSD-capable plastics in particular.
Morphological studies of sulfonated polystyrene and sulfonated EPDM ionomers
DOE Office of Scientific and Technical Information (OSTI.GOV)
Jackson, D.A.
1992-12-31
Two ionomer systems have been investigated in this research. Sulfonated polystyrene (SPS) is a typical random ionomer and is a good material for studies into the nature of phase separation in ionomers. A series of narrow molecular weight distribution (MWD) zinc neutralized SPS samples of varying sulfonation levels were prepared and analyzed through small angle x-ray scattering (SAXS). Results indicated that the correlation distance varied with both molecular weight and sulfonation level. Increases in the position of the scattering maximum with sulfonation level is the result of a greater number of ionic groups. Increasing molecular weight led to the movementmore » of the scattering maximum to smaller scattering vectors, an indication of larger distances. It was also observed that ionomer peak occurred at smaller scattering vectors for the narrow MWD samples than in corresponding materials of greater dispersity. SAXS was also used to examine the morphology of zinc stearate (ZnSt) filled sulfonated EPDM (S-EPDM) ionomers and the nature of the interaction between the plasticizer and the ionomer. S-EPDM is a material that may find use as a thermoplastic elastomer, although its melt viscosity is too high to allow for convenient processing. The addition of of ZnSt as a plasticizer greatly reduces the melt viscosity of S-EPDM. ZnSt exists in this system as very small crystallites which are associated with ionic groups. As the temperature is increased, the crystallites anneal briefly into larger crystals before melting and diffusing into the S-EPDM matrix. Above the melting temperature of the ZnSt, it solvates the ionic groups of the ionomer, decreasing their self-association and the viscosity of the system. Increasing ZnSt loading is seen in the SAXS as an increase in scattering in the low angle region. However, this increase in intensity is not linear with concentration, showing that ZnSt exists in different environments at higher concentrations.« less
Acosta-García, Ma Cristina; Morales-Reyes, Israel; Jiménez-Anguiano, Anabel; Batina, Nikola; Castellanos, N P; Godínez-Fernández, R
2018-02-01
This paper shows the simultaneous recording of electrical activity and the underlying ionic currents by using a gold substrate to culture NG108-15 cells. Cells grown on two different substrates (plastic Petri dishes and gold substrates) were characterized quantitatively through scanning electron microscopy (SEM) as well as qualitatively by optical and atomic force microscopy (AFM). No significant differences were observed between the surface area of cells cultured on gold substrates and Petri dishes, as indicated by measurements performed on SEM images. We also evaluated the electrophysiological compatibility of the cells through standard patch-clamp experiments by analyzing features such as the resting potential, membrane resistance, ionic currents, etc. Cells grown on both substrates showed no significant differences in their dependency on voltage, as well as in the magnitude of the Na+ and K+ current density; however, cells cultured on the gold substrate showed a lower membrane capacitance when compared to those grown on Petri dishes. By using two separate patch-clamp amplifiers, we were able to record the membrane current with the conventional patch-clamp technique and through the gold substrate simultaneously. Furthermore, the proposed technique allowed us to obtain simultaneous recordings of the electrical activity (such as action potentials firing) and the underlying membrane ionic currents. The excellent conductivity of gold makes it possible to overcome important difficulties found in conventional electrophysiological experiments such as those presented by the resistance of the electrolytic bath solution. We conclude that the technique here presented constitutes a solution to the problem of the simultaneous recording of electrical activity and the underlying ionic currents, which for decades, had been solved only partially.
An experimental study on PEO polymer electrolyte based all-solid-state supercapacitor
NASA Astrophysics Data System (ADS)
Yijing, Yin
Supercapacitors are one of the most important electrochemical energy storage and conversion devices, however low ionic conductivity of solid state polymer electrolytes and the poor accessibility of the ions to the active sites in the porous electrode will cause low performance for all-solid-state supercapacitors and will limit their application. The objective of the dissertation is to improve the performance of all-solid-state supercapactor by improving electrolyte conductivity and solving accessibility problem of the ions to the active sites. The low ionic conductivity (10-8 S/cm) of poly(ethylene oxide) (PEO) limits its application as an electrolyte. Since PEO is a semicrystal polymer and the ion conduction take place mainly in the amorphous regions of the PEO/Lithium salt complex, improvements in the percentage of amorphous phase in PEO or increasing the charge carrier concentration and mobility could increase the ionic conductivity of PEO electrolyte. Hot pressing along with the additions of different lithium salts, inorganic fillers and plasticizers were applied to improve the ionic conductivity of PEO polymer electrolytes. Four electrode methods were used to evaluate the conductivity of PEO based polymer electrolytes. Results show that adding certain lithium salts, inorganic fillers, and plasticizers could improve the ionic conductivity of PEO electrolytes up 10-4 S/cm. Further hot pressing treatment could improve the ionic conductivity of PEO electrolytes up to 10-3 S/cm. The conductivity improvement after hot pressing treatment is elucidated as that the spherulite crystal phase is convert into the fringed micelle crystal phase or the amorphous phase of PEO electrolytes. PEO electrolytes were added into active carbon as a binder and an ion conductor, so as to provide electrodes with not only ion conduction, but also the accessibility of ion to the active sites of electrodes. The NaI/I 2 mediator was added to improve the conductivity of PEO electrolyte and provide pseudocapacitance for all-solid-state supercapacitors. Impedance, cyclic voltammetry, and gavalnostatic charge/discharge measurements were conducted to evaluate the electrochemical performance of PEO polymer electrolytes based all-solid-state supercapacitors. Results demonstrate that the conductivity of PEO electrolyte could be improved to 0.1 S/cm with a mediator concentration of 50wt%. A high conductivity in the PEO electrolyte with mediator is an indication of a high electron exchange rate between the mediator and mediator. The high electron exchange rates at mediator carbon interface and between mediator and mediator are essential in order to obtain a high response rate and high power. This automatically solves the accessibility problem. With the addition of NaI/I2 mediator, the specific capacitance increased more than 30 folds, specific power increased almost 20 folds, and specific energy increased around 10 folds. Further addition of filler to the electrodes along with the mediator could double the specific capacitor and specific power of the all-solid-state supercapacitor. The stability of the corresponded supercapacitor is good within 2000 cycles.
Lombardi, Sara A; Hicks, Reimi E; Thompson, Katerina V; Marbach-Ad, Gili
2014-03-01
This study investigated the impact of three commonly used cardiovascular model-assisted activities on student learning and student attitudes and perspectives about science. College students enrolled in a Human Anatomy and Physiology course were randomly assigned to one of three experimental groups (organ dissections, virtual dissections, or plastic models). Each group received a 15-min lecture followed by a 45-min activity with one of the treatments. Immediately after the lesson and then 2 mo later, students were tested on anatomy and physiology knowledge and completed an attitude survey. Students who used plastic models achieved significantly higher overall scores on both the initial and followup exams than students who performed organ or virtual dissections. On the initial exam, students in the plastic model and organ dissection treatments scored higher on anatomy questions than students who performed virtual dissections. Students in the plastic model group scored higher than students who performed organ dissections on physiology questions. On the followup exam, when asked anatomy questions, students in the plastic model group scored higher than dissection students and virtual dissection students. On attitude surveys, organ dissections had higher perceived value and were requested for inclusion in curricula twice as often as any other activity. Students who performed organ dissections were more likely than the other treatment groups to agree with the statement that "science is fun," suggesting that organ dissections may promote positive attitudes toward science. The findings of this study provide evidence for the importance of multiple types of hands-on activities in anatomy laboratory courses.
Ionic liquid technology to recover volatile organic compounds (VOCs).
Salar-García, M J; Ortiz-Martínez, V M; Hernández-Fernández, F J; de Los Ríos, A P; Quesada-Medina, J
2017-01-05
Volatile organic compounds (VOCs) comprise a wide variety of carbon-based materials which are volatile at relatively low temperatures. Most of VOCs pose a hazard to both human health and the environment. For this reason, in the last years, big efforts have been made to develop efficient techniques for the recovery of VOCs produced from industry. The use of ionic liquids (ILs) is among the most promising separation technologies in this field. This article offers a critical overview on the use of ionic liquids for the separation of VOCs both in bulk and in immobilized form. It covers the most relevant works within this field and provides a global outlook on the limitations and future prospects of this technology. The extraction processes of VOCs by using different IL-based assemblies are described in detail and compared with conventional methods This review also underlines the advantages and limitations posed by ionic liquids according to the nature of the cation and the anions present in their structure and the stability of the membrane configurations in which ILs are used as liquid phase. Copyright © 2016 Elsevier B.V. All rights reserved.
Static and dynamic wetting behaviour of ionic liquids.
Delcheva, Iliana; Ralston, John; Beattie, David A; Krasowska, Marta
2015-08-01
Ionic liquids (ILs) are a unique family of molecular liquids ('molten salts') that consist of a combination of bulky organic cations coupled to inorganic or organic anions. The net result of steric hindrance and strong hydrogen bonding between components results in a material that is liquid at room temperature. One can alter the properties of ionic liquids through chemical modification of anion and cation, thus tailoring the IL for a given application. One such property that can be controlled or selected is the wettability of an IL on a particular solid substrate. However, the study of wetting of ionic liquids is complicated by the care required for accurate and reproducible measurement, due to both the susceptibility of the IL properties to water content, as well as to the sensitivity of wettability measurements to the state of the solid surface. This review deals with wetting studies of ILs to date, including both static and dynamic wetting, as well as issues concerning line tension and the formation of precursor and wetting films. Copyright © 2014 Elsevier B.V. All rights reserved.
Vermeiren, Peter; Muñoz, Cynthia C; Ikejima, Kou
2016-12-15
Micro- and macroplastic accumulation threatens estuaries worldwide because of the often dense human populations, diverse plastic inputs and high potential for plastic degradation and storage in these ecosystems. Nonetheless, our understanding of plastic sources and sinks remains limited. We designed conceptual models of the local and estuary-wide transport of plastics. We identify processes affecting the position of plastics in the water column; processes related to the mixing of fresh and salt water; and processes resulting from the influences of wind, topography, and organism-plastic interactions. The models identify gaps in the spatial context of plastic-organisms interactions, the chemical behavior of plastics in estuaries, effects of wind on plastic suspension-deposition cycles, and the relative importance of processes affecting the position in the water column. When interpreted in the context of current understanding, sinks with high management potential can be identified. However, source-sink patterns vary among estuary types and with local scale processes. Copyright © 2016 Elsevier Ltd. All rights reserved.
Ver Halen, Jon P; Chen, Andrew; Jeffers, Lynn; Basu, C Bob
2014-08-01
Given the continued evolution of the American health system, the authors explored young plastic surgeons' attitudes on challenges affecting the specialty and the future role of organized plastic surgery and its advocacy mission. A 21-question online survey was distributed to all members of the Young Plastic Surgeons Forum. Questions were related to demographics, attitudes toward policy issues, participation in the American Society of Plastic Surgeons, and its advocacy efforts. The survey was e-mailed to 2155 Forum members, of which 397 responded (19% response rate). Young plastic surgeons appear to be interested in American Society of Plastic Surgeons and PlastyPAC, as evidenced by a higher than normal response rate to this survey and rate of contribution. However, a lack of awareness about the details of the organizations and mechanisms for involvement remains. Scope-of-practice issues and encroachment on the specialty by noncore providers remain the top concern of young plastic surgeons. Other top concerns were financial barriers to participation in advocacy efforts and concerns with return on investment on PlastyPAC contributions. A majority received minimal or no public policy education on issues affecting plastic surgery during training. A minority currently participate in American Society of Plastic Surgeons advocacy efforts. These data represent the first such collection of opinions from Young Plastic Surgeons members regarding goals and directions of the American Society of Plastic Surgeons and PlastyPAC. These organizations are in a uniquely strong position to enlist participation from and provide for the future success of the profession's younger members.
Aza-crown ether complex cation ionic liquids: preparation and applications in organic reactions.
Song, Yingying; Cheng, Chen; Jing, Huanwang
2014-09-26
Aza-crown ether complex cation ionic liquids (aCECILs) were devised, fabricated, and characterized by using NMR spectroscopy, MS, thermogravimetric differential thermal analysis (TG-DTA), elemental analysis and physical properties. These new and room-temperature ILs were utilized as catalysts in various organic reactions, such as the cycloaddition reaction of CO2 to epoxides, esterification of acetic acid and alcohols, the condensation reaction of aniline and propylene carbonate, and Friedel-Crafts alkylation of indole with aldehydes were investigated carefully. In these reactions, the ionic liquid exhibited cooperative catalytic activity between the anion and cation. In addition, the aza-[18-C-6HK][HSO4]2 was the best acidic catalyst in the reactions of esterification and Friedel-Crafts alkylation under mild reaction conditions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Bozym, David J; Uralcan, Betül; Limmer, David T; Pope, Michael A; Szamreta, Nicholas J; Debenedetti, Pablo G; Aksay, Ilhan A
2015-07-02
We use electrochemical impedance spectroscopy to measure the effect of diluting a hydrophobic room temperature ionic liquid with miscible organic solvents on the differential capacitance of the glassy carbon-electrolyte interface. We show that the minimum differential capacitance increases with dilution and reaches a maximum value at ionic liquid contents near 5-10 mol% (i.e., ∼1 M). We provide evidence that mixtures with 1,2-dichloroethane, a low-dielectric constant solvent, yield the largest gains in capacitance near the open circuit potential when compared against two traditional solvents, acetonitrile and propylene carbonate. To provide a fundamental basis for these observations, we use a coarse-grained model to relate structural variations at the double layer to the occurrence of the maximum. Our results reveal the potential for the enhancement of double-layer capacitance through dilution.
CuS nanoplates from ionic liquid precursors—Application in organic photovoltaic cells
NASA Astrophysics Data System (ADS)
Kim, Yohan; Heyne, Benjamin; Abouserie, Ahed; Pries, Christopher; Ippen, Christian; Günter, Christina; Taubert, Andreas; Wedel, Armin
2018-05-01
Hexagonal p-type semiconductor CuS nanoplates were synthesized via a hot injection method from bis(trimethylsilyl)sulfide and the ionic liquid precursor bis(N-dodecylpyridinium) tetrachloridocuprate(ii). The particles have a broad size distribution with diameters between 30 and 680 nm and well-developed crystal habits. The nanoplates were successfully incorporated into organic photovoltaic (OPV) cells as hole conduction materials. The power conversion efficiency of OPV cells fabricated with the nanoplates is 16% higher than that of a control device fabricated without the nanoplates.
Millimeter-sized marine plastics: a new pelagic habitat for microorganisms and invertebrates.
Reisser, Julia; Shaw, Jeremy; Hallegraeff, Gustaaf; Proietti, Maira; Barnes, David K A; Thums, Michele; Wilcox, Chris; Hardesty, Britta Denise; Pattiaratchi, Charitha
2014-01-01
Millimeter-sized plastics are abundant in most marine surface waters, and known to carry fouling organisms that potentially play key roles in the fate and ecological impacts of plastic pollution. In this study we used scanning electron microscopy to characterize biodiversity of organisms on the surface of 68 small floating plastics (length range = 1.7-24.3 mm, median = 3.2 mm) from Australia-wide coastal and oceanic, tropical to temperate sample collections. Diatoms were the most diverse group of plastic colonizers, represented by 14 genera. We also recorded 'epiplastic' coccolithophores (7 genera), bryozoans, barnacles (Lepas spp.), a dinoflagellate (Ceratium), an isopod (Asellota), a marine worm, marine insect eggs (Halobates sp.), as well as rounded, elongated, and spiral cells putatively identified as bacteria, cyanobacteria, and fungi. Furthermore, we observed a variety of plastic surface microtextures, including pits and grooves conforming to the shape of microorganisms, suggesting that biota may play an important role in plastic degradation. This study highlights how anthropogenic millimeter-sized polymers have created a new pelagic habitat for microorganisms and invertebrates. The ecological ramifications of this phenomenon for marine organism dispersal, ocean productivity, and biotransfer of plastic-associated pollutants, remains to be elucidated.
Millimeter-Sized Marine Plastics: A New Pelagic Habitat for Microorganisms and Invertebrates
Reisser, Julia; Shaw, Jeremy; Hallegraeff, Gustaaf; Proietti, Maira; Barnes, David K. A.; Thums, Michele; Wilcox, Chris; Hardesty, Britta Denise; Pattiaratchi, Charitha
2014-01-01
Millimeter-sized plastics are abundant in most marine surface waters, and known to carry fouling organisms that potentially play key roles in the fate and ecological impacts of plastic pollution. In this study we used scanning electron microscopy to characterize biodiversity of organisms on the surface of 68 small floating plastics (length range = 1.7–24.3 mm, median = 3.2 mm) from Australia-wide coastal and oceanic, tropical to temperate sample collections. Diatoms were the most diverse group of plastic colonizers, represented by 14 genera. We also recorded ‘epiplastic’ coccolithophores (7 genera), bryozoans, barnacles (Lepas spp.), a dinoflagellate (Ceratium), an isopod (Asellota), a marine worm, marine insect eggs (Halobates sp.), as well as rounded, elongated, and spiral cells putatively identified as bacteria, cyanobacteria, and fungi. Furthermore, we observed a variety of plastic surface microtextures, including pits and grooves conforming to the shape of microorganisms, suggesting that biota may play an important role in plastic degradation. This study highlights how anthropogenic millimeter-sized polymers have created a new pelagic habitat for microorganisms and invertebrates. The ecological ramifications of this phenomenon for marine organism dispersal, ocean productivity, and biotransfer of plastic-associated pollutants, remains to be elucidated. PMID:24941218
Fugacity analysis of polycyclic aromatic hydrocarbons between microplastics and seawater
NASA Astrophysics Data System (ADS)
Lee, Hwang; Chang, Sein; Kim, Seung-Kyu; Kwon, Jung-Hwan
2017-03-01
Recently, the accumulation of plastic debris in the marine environment has become a great concern worldwide. Although plastics are biologically and chemically inert, plastic debris has been suspected of causing adverse effects on ecosystems due to the increase in reactivity by size reduction and/or micropollutants associated with plastics. Because of the high sorption capacity of microplastics toward organic micropollutants, it is suspected that microplastics may play roles in the distribution and fate of micropollutants. In order to quantitatively evaluate the "net flow" of environmental contaminants in water-plastic-organism systems, a fugacity analysis was conducted using concentrations of polycyclic aromatic hydrocarbons (PAHs) in open oceans and in polyethylene as a representative material of plastic debris. Ratio of fugacity in polyethylene to that in seawater showed a decreasing trend with increasing partition coefficient between polyethylene and seawater (KPE/sw). This indicates that phase equilibrium between polyethylene and seawater is not attained for higher molecular weight PAHs. Disequilibrium of high molecular weight PAHs suggests that transfer from seawater to plastic debris is thermodynamically driven and the role of plastic debris as a vector to transfer them to living organisms would be minimal. However, additives may slowly migrate from plastics into the environment causing potentially serious effects on ecosystems.
Study on the Characteristics of a Scintillator for Beta-ray Detection using Epoxy Resin
NASA Astrophysics Data System (ADS)
Nam, Jong Soo; Choi, Yong Seok; Hong, Sang Bum; Seo, Bum Kyung; Moon, Jei Kwon; Choi, Jong Won
2017-09-01
A thin plate of a plastic scintillator for detecting a beta-ray was developed. The plastic scintillator was made using epoxy resin and organic scintillators such as 2.5-diphenyloxazole (PPO) and 1,4-bis [5-phenyl-2-oxazole] benzene (POPOP). The mixture ratio of epoxy resin and the organic scintillators was determined using their absorbance, transmittance, emission spectra, and transparency. Their optimal weight percentage of PPO and POPOP in the organic scintillators was adjusted to 0.2 wt%:0.01 wt%. The prepared plastic scintillator was used to measure the standard source of Sr-90. The pulse height spectra and total counts of the prepared plastic scintillator were similar to a commercial plastic scintillator. Based on the above results, a large-area plastic scintillator was prepared for rapid investigation of a site contaminated with Sr-90. The prepared large-area plastic scintillator was evaluated for the characteristics in the laboratory. The evaluation results are expected to be usefully utilized in the development of a large-area plastic scintillation detector. The large-area plastic scintillation detector developed on the basis of the evaluation results is expected to be utilized to quickly measure the contamination of Sr-90 in the grounds used as a nuclear power facility.
Gao, Tingting; Andino, Jean M; Alvarez-Idaboy, J Raul
2010-09-07
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.
40 CFR 414.11 - Applicability.
Code of Federal Regulations, 2010 CFR
2010-07-01
... ORGANIC CHEMICALS, PLASTICS, AND SYNTHETIC FIBERS General § 414.11 Applicability. (a) The provisions of... establishments that manufacture the organic chemicals, plastics, and synthetic fibers (OCPSF) products or product...-Made Fibers, (3) SIC 2824—Synthetic Organic Fibers, Except Cellulosic, (4) SIC 2865—Cyclic Crudes and...
Haftka, Joris J-H; Scherpenisse, Peter; Jonker, Michiel T O; Hermens, Joop L M
2013-05-07
A passive sampling method using polyacrylate-coated solid-phase microextraction (SPME) fibers was applied to determine sorption of polar and ionic organic contaminants to dissolved organic carbon (DOC). The tested contaminants included pharmaceuticals, industrial chemicals, hormones, and pesticides and represented neutral, anionic, and cationic structures. Prior to the passive sampler application, sorption of the chemicals to the fibers was characterized. This was needed in order to accurately translate concentrations measured in fibers to freely dissolved aqueous concentrations during the sorption tests with DOC. Sorption isotherms of neutral compounds to the fiber were linear, whereas isotherms of basic chemicals covered a nonlinear and a linear range. Sorption of acidic and basic compounds to the fiber was pH-dependent and was dominated by sorption of the neutral sorbate species. Fiber- and DOC-water partition coefficients of neutral compounds were both linearly related to octanol-water partition coefficients (log Kow). The results of this study show that polyacrylate fibers can be used to quantify sorption to DOC of neutral and ionic contaminants, having multiple functional groups and spanning a wide hydrophobicity range (log Kow = 2.5-7.5).
Piotrowska, Aleksandra; Syguda, Anna; Wyrwas, Bogdan; Chrzanowski, Lukasz; Luckenbach, Till; Heipieper, Hermann J
2018-01-01
Ionic liquids consisting of a combination of herbicidal anions with a quaternary ammonium cation act as efficient herbicides, which are under consideration to be used in the agriculture. In the present study, we used embryos of the zebrafish (Danio rerio) as a model to assess the toxic potential of ammonium-based ionic liquids for aquatic organisms. As we assumed interference of the partially hydrophobic ionic liquid cation with lipids, we investigated the adaptation response in the lipid composition of the zebrafish embryos, triggered by the ionic compound. Therefore, the impact of ammonium-based ionic liquids with different lengths of the alkyl chain ([C6,C6,C1,C1N][Br], [C8,C8,C1,C1N][Br]) on the phospholipid fatty acid (PLFA) profile of zebrafish embryos up to 72 hours post fertilization (hpf) was examined. Furthermore, the changes in the unsaturation index (UI) of PLFAs, as the sum parameter of membrane fluidity in eukaryotic cells, were presented. The PLFA's UI in the zebrafish embryos upon exposure to quaternary ammonium salts was compared to the UI of the embryos upon exposure to nonionic 2,4-dichlorophenol, which has a similar hydrophobicity but is structurally different to [C8,C8,C1,C1N][Br]. It was shown that for ammonium-based ionic liquid precursors non-specific mode of action occurs and the toxic effect on lipid composition of zebrafish embryos can be well predicted based on chemical properties, like hydrophobicity. Furthermore, the changes in PLFAs, expressed by the UI, can be useful to study toxic effects of organic contamination. However, for zebrafish embryos, after ionic liquids and 2,4-DCP exposure, the changes were observed at high lethal concentrations, which caused the incidence of lethality of 30 and 50% of a group of test animals.
Piotrowska, Aleksandra; Syguda, Anna; Wyrwas, Bogdan; Chrzanowski, Lukasz; Luckenbach, Till
2018-01-01
Ionic liquids consisting of a combination of herbicidal anions with a quaternary ammonium cation act as efficient herbicides, which are under consideration to be used in the agriculture. In the present study, we used embryos of the zebrafish (Danio rerio) as a model to assess the toxic potential of ammonium-based ionic liquids for aquatic organisms. As we assumed interference of the partially hydrophobic ionic liquid cation with lipids, we investigated the adaptation response in the lipid composition of the zebrafish embryos, triggered by the ionic compound. Therefore, the impact of ammonium-based ionic liquids with different lengths of the alkyl chain ([C6,C6,C1,C1N][Br], [C8,C8,C1,C1N][Br]) on the phospholipid fatty acid (PLFA) profile of zebrafish embryos up to 72 hours post fertilization (hpf) was examined. Furthermore, the changes in the unsaturation index (UI) of PLFAs, as the sum parameter of membrane fluidity in eukaryotic cells, were presented. The PLFA’s UI in the zebrafish embryos upon exposure to quaternary ammonium salts was compared to the UI of the embryos upon exposure to nonionic 2,4-dichlorophenol, which has a similar hydrophobicity but is structurally different to [C8,C8,C1,C1N][Br]. It was shown that for ammonium-based ionic liquid precursors non-specific mode of action occurs and the toxic effect on lipid composition of zebrafish embryos can be well predicted based on chemical properties, like hydrophobicity. Furthermore, the changes in PLFAs, expressed by the UI, can be useful to study toxic effects of organic contamination. However, for zebrafish embryos, after ionic liquids and 2,4-DCP exposure, the changes were observed at high lethal concentrations, which caused the incidence of lethality of 30 and 50% of a group of test animals. PMID:29342167
Mattsson, Karin; Johnson, Elyse V; Malmendal, Anders; Linse, Sara; Hansson, Lars-Anders; Cedervall, Tommy
2017-09-13
The tremendous increases in production of plastic materials has led to an accumulation of plastic pollution worldwide. Many studies have addressed the physical effects of large-sized plastics on organisms, whereas few have focused on plastic nanoparticles, despite their distinct chemical, physical and mechanical properties. Hence our understanding of their effects on ecosystem function, behaviour and metabolism of organisms remains elusive. Here we demonstrate that plastic nanoparticles reduce survival of aquatic zooplankton and penetrate the blood-to-brain barrier in fish and cause behavioural disorders. Hence, for the first time, we uncover direct interactions between plastic nanoparticles and brain tissue, which is the likely mechanism behind the observed behavioural disorders in the top consumer. In a broader perspective, our findings demonstrate that plastic nanoparticles are transferred up through a food chain, enter the brain of the top consumer and affect its behaviour, thereby severely disrupting the function of natural ecosystems.
Dissolved organic carbon leaching from plastics stimulates microbial activity in the ocean.
Romera-Castillo, Cristina; Pinto, Maria; Langer, Teresa M; Álvarez-Salgado, Xosé Antón; Herndl, Gerhard J
2018-04-12
Approximately 5.25 trillion plastic pieces are floating at the sea surface. The impact of plastic pollution on the lowest trophic levels of the food web, however, remains unknown. Here we show that plastics release dissolved organic carbon (DOC) into the ambient seawater stimulating the activity of heterotrophic microbes. Our estimates indicate that globally up to 23,600 metric tons of DOC are leaching from marine plastics annually. About 60% of it is available to microbial utilization in less than 5 days. If exposed to solar radiation, however, this DOC becomes less labile. Thus, plastic pollution of marine surface waters likely alters the composition and activity of the base of the marine food webs. It is predicted that plastic waste entering the ocean will increase by a factor of ten within the next decade, resulting in an increase in plastic-derived DOC that might have unaccounted consequences for marine microbes and for the ocean system.
Plastic waste in the marine environment: A review of sources, occurrence and effects.
Li, W C; Tse, H F; Fok, L
2016-10-01
This review article summarises the sources, occurrence, fate and effects of plastic waste in the marine environment. Due to its resistance to degradation, most plastic debris will persist in the environment for centuries and may be transported far from its source, including great distances out to sea. Land- and ocean-based sources are the major sources of plastic entering the environment, with domestic, industrial and fishing activities being the most important contributors. Ocean gyres are particular hotspots of plastic waste accumulation. Both macroplastics and microplastics pose a risk to organisms in the natural environment, for example, through ingestion or entanglement in the plastic. Many studies have investigated the potential uptake of hydrophobic contaminants, which can then bioaccumulate in the food chain, from plastic waste by organisms. To address the issue of plastic pollution in the marine environment, governments should first play an active role in addressing the issue of plastic waste by introducing legislation to control the sources of plastic debris and the use of plastic additives. In addition, plastics industries should take responsibility for the end-of-life of their products by introducing plastic recycling or upgrading programmes. Copyright © 2016 Elsevier B.V. All rights reserved.
Plastic Organic Scintillator Chemistry
NASA Astrophysics Data System (ADS)
Brightwell, C. R.; Temanson, E. S.; Febbraro, M. T.
2017-09-01
Due to their high light output, quick decay time, affordability, durability and ability to be molded, plastic organic scintillators are increasingly becoming a more viable method of particle detection. Since the plastic is composed entirely of single molecular chains with repeating units, scintillating properties remain stable despite changes in experimental conditions. Different scintillating plastics can be modified and tailored to suit specific experiments depending on a variety of requirements such as light output, scintillating wavelength, and PMT compatibility. The synthesis chemistry of a recent but well-known scintillating polyester, polyethylene naphthalate (PEN) will be presented to demonstrate how plastic organic scintillators can be modified for different particle detection experiments. PEN has been successfully synthesized at ORNL, and procedures are currently being investigated to modify PEN using different reactants and catalysts. The goal is to achieve a transparent scintillating plastic with an incorporated wavelength shifter in the chain that scintillates with a wavelength around 440 nm. The status of this project will be presented. This research is supported by the U. S. Department of Energy Office of Science.
Waterborne Diseases & Illnesses
... Lead Arsenic Volatile Organic Compounds Plastics Pesticides Climate Change Climate Change Home What is Climate Change Greenhouse Gases ... Lead Arsenic Volatile Organic Compounds Plastics Pesticides Climate Change Climate Change Home What is Climate Change Greenhouse Gases ...
Molecular Approach to Conjugated Polymers with Biomimetic Properties.
Baek, Paul; Voorhaar, Lenny; Barker, David; Travas-Sejdic, Jadranka
2018-06-13
The field of bioelectronics involves the fascinating interplay between biology and human-made electronics. Applications such as tissue engineering, biosensing, drug delivery, and wearable electronics require biomimetic materials that can translate the physiological and chemical processes of biological systems, such as organs, tissues. and cells, into electrical signals and vice versa. However, the difference in the physical nature of soft biological elements and rigid electronic materials calls for new conductive or electroactive materials with added biomimetic properties that can bridge the gap. Soft electronics that utilize organic materials, such as conjugated polymers, can bring many important features to bioelectronics. Among the many advantages of conjugated polymers, the ability to modulate the biocompatibility, solubility, functionality, and mechanical properties through side chain engineering can alleviate the issues of mechanical mismatch and provide better interface between the electronics and biological elements. Additionally, conjugated polymers, being both ionically and electrically conductive through reversible doping processes provide means for direct sensing and stimulation of biological processes in cells, tissues, and organs. In this Account, we focus on our recent progress in molecular engineering of conjugated polymers with tunable biomimetic properties, such as biocompatibility, responsiveness, stretchability, self-healing, and adhesion. Our approach is general and versatile, which is based on functionalization of conjugated polymers with long side chains, commonly polymeric or biomolecules. Applications for such materials are wide-ranging, where we have demonstrated conductive, stimuli-responsive antifouling, and cell adhesive biointerfaces that can respond to external stimuli such as temperature, salt concentration, and redox reactions, the processes that in turn modify and reversibly switch the surface properties. Furthermore, utilizing the advantageous chemical, physical, mechanical and functional properties of the grafts, we progressed into grafting of the long side chains onto conjugated polymers in solution, with the vision of synthesizing solution-processable conjugated graft copolymers with biomimetic functionalities. Examples of the developed materials to date include rubbery and adhesive photoluminescent plastics, biomolecule-functionalized electrospun biosensors, thermally and dually responsive photoluminescent conjugated polymers, and tunable self-healing, adhesive, and stretchable strain sensors, advanced functional biocidal polymers, and filtration membranes. As outlined in these examples, the applications of these biomimetic, conjugated polymers are still in the development stage toward truly printable, organic bioelectronic devices. However, in this Account, we advocate that molecular engineering of conjugated polymers is an attractive approach to a versatile class of organic electronics with both ionic and electrical conductivity as well as mechanical properties required for next-generation bioelectronics.
Li, Heng-Xiang; Getzinger, Gordon J; Ferguson, P Lee; Orihuela, Beatriz; Zhu, Mei; Rittschof, Daniel
2016-01-19
Plastic pollution represents a major and growing global problem. It is well-known that plastics are a source of chemical contaminants to the aquatic environment and provide novel habitats for marine organisms. The present study quantified the impacts of plastic leachates from the seven categories of recyclable plastics on larval survival and settlement of barnacle Amphibalanus (=Balanus) amphitrite. Leachates from plastics significantly increased barnacle nauplii mortality at the highest tested concentrations (0.10 and 0.50 m(2)/L). Hydrophobicity (measured as surface energy) was positively correlated with mortality indicating that plastic surface chemistry may be an important factor in the effects of plastics on sessile organisms. Plastic leachates significantly inhibited barnacle cyprids settlement on glass at all tested concentrations. Settlement on plastic surfaces was significantly inhibited after 24 and 48 h, but settlement was not significantly inhibited compared to the controls for some plastics after 72-96 h. In 24 h exposure to seawater, we found larval toxicity and inhibition of settlement with all seven categories of recyclable commercial plastics. Chemical analysis revealed a complex mixture of substances released in plastic leachates. Leaching of toxic compounds from all plastics should be considered when assessing the risks of plastic pollution.
APPLICATION OF THE MASTER ANALYTICAL SCHEME TO POLAR ORGANICS IN DRINKING WATER
EPA's Master Analytical Scheme (MAS) for Organic Compounds in Water provides for comprehensive qualitative-quantitative analysis of gas chromatographable organics in many types of water. The paper emphasizes the analysis of polar and ionic organics, the more water soluble compoun...
Microplastic ingestion by Daphnia magna and its enhancement on algal growth.
Canniff, Patrick M; Hoang, Tham C
2018-08-15
The rapid increase in plastic use over the last few decades has resulted in plastic pollution in freshwater and marine ecosystems. However, more attention has been paid to plastic pollution in marine ecosystems than to freshwater ecosystems. This research determined microplastic ingestion by Daphnia magna and the potential effect of microplastics on the organism's survival and reproduction. The study also examined the potential of microplastics to enhance algal growth in support of understanding effects of microplastic ingestion on the organism. When exposed to 25, 50, and 100mg/L fluorescent green polyethylene microbeads at size of 63-75μm, D. magna ingested significant amount of plastic microbeads. The number of ingested beads increased with increasing particle concentration and exposure time. However, no significant effect on survival and reproduction was observed although the gut of D. magna was filled with plastic microbeads. In the algal experiment, Raphidocelis subcapitata grew more in the exposure media with the present of plastic microbeads than without plastic microbeads. This result suggests that plastic microbeads could serve as substrates for R. subcapitata to grow. Raphidocelis subcapitata then could be transferred to the organism's gut and provided energy for survival and reproduction. Results of the present study add to the literature of microplastic ingestion by aquatic organisms. Caution should be taken when interpreting hazards of microplastics based on ingestion, such as the measurement unit and the presence of algae in the environment. Copyright © 2018 Elsevier B.V. All rights reserved.
Self‐Regulative Nanogelator Solid Electrolyte: A New Option to Improve the Safety of Lithium Battery
Wu, Feng; Chen, Nan; Zhu, Qizhen; Tan, Guoqiang; Li, Li
2016-01-01
The lack of suitable nonflammable electrolytes has delayed battery application in electric vehicles. A new approach to improve the safety performance for lithium battery is proposed here. This technology is based on a nanogelator‐based solid electrolyte made of porous oxides and an ionic liquid. The electrolyte is fabricated using an in situ method and the porous oxides serve as a nonflammable “nanogelator” that spontaneously immobilizes the ionic liquid. The electrolyte exhibits a high liquid‐like apparent ionic conductivity of 2.93 × 10−3 S cm−1 at room temperature. The results show that the nanogelator, which possess self‐regulating ability, is able to immobilize imidazolium‐, pyrrolidinium‐, or piperidinium‐based ionic liquids, simply by adjusting the ion transport channels. Our prototype batteries made of Ti‐nanogeltor solid electrolyte outperform conventional lithium batteries made using ionic liquid and commercial organic liquid electrolytes. PMID:27774385
Wu, Feng; Chen, Nan; Chen, Renjie; Zhu, Qizhen; Tan, Guoqiang; Li, Li
2016-01-01
The lack of suitable nonflammable electrolytes has delayed battery application in electric vehicles. A new approach to improve the safety performance for lithium battery is proposed here. This technology is based on a nanogelator-based solid electrolyte made of porous oxides and an ionic liquid. The electrolyte is fabricated using an in situ method and the porous oxides serve as a nonflammable "nanogelator" that spontaneously immobilizes the ionic liquid. The electrolyte exhibits a high liquid-like apparent ionic conductivity of 2.93 × 10 -3 S cm -1 at room temperature. The results show that the nanogelator, which possess self-regulating ability, is able to immobilize imidazolium-, pyrrolidinium-, or piperidinium-based ionic liquids, simply by adjusting the ion transport channels. Our prototype batteries made of Ti-nanogeltor solid electrolyte outperform conventional lithium batteries made using ionic liquid and commercial organic liquid electrolytes.
Arsenic (Environmental Health Student Portal)
... Lead Arsenic Volatile Organic Compounds Plastics Pesticides Climate Change Climate Change Home What is Climate Change Greenhouse Gases ... Lead Arsenic Volatile Organic Compounds Plastics Pesticides Climate Change Climate Change Home What is Climate Change Greenhouse Gases ...
INORGANIC AND ORGANIC ONIUM SALTS
The nitrosonium NO ion absorbs in the infrared between 1/2400 and 1/ 2150 cm. Salts of complex fluoro-acids absorb at higher frequencies than salts...halide adducts generally contain nitrosonium ions . Hexaphenylditin does not undergo marked heterolytic dissociation in nitromethane solution...influencing the covalent-ionic equilibrium are discussed. Infrared spectrum nitrosonium ion ; ionic character in lattice and position nitrosonium ion absorption
Immobilization of molecular catalysts in supported ionic liquid phases.
Van Doorslaer, Charlie; Wahlen, Joos; Mertens, Pascal; Binnemans, Koen; De Vos, Dirk
2010-09-28
In a supported ionic liquid phase (SILP) catalyst system, an ionic liquid (IL) film is immobilized on a high-surface area porous solid and a homogeneous catalyst is dissolved in this supported IL layer, thereby combining the attractive features of homogeneous catalysts with the benefits of heterogeneous catalysts. In this review reliable strategies for the immobilization of molecular catalysts in SILPs are surveyed. In the first part, general aspects concerning the application of SILP catalysts are presented, focusing on the type of catalyst, support, ionic liquid and reaction conditions. Secondly, organic reactions in which SILP technology is applied to improve the performance of homogeneous transition-metal catalysts are presented: hydroformylation, metathesis reactions, carbonylation, hydrogenation, hydroamination, coupling reactions and asymmetric reactions.
75 FR 29974 - Application(s) for Duty-Free Entry of Scientific Instruments
Federal Register 2010, 2011, 2012, 2013, 2014
2010-05-28
... portions of vertebrate and invertebrate organisms embedded in plastic resins and cut into thin sections... vertebrate and invertebrate organisms embedded in plastic resins and cut into thin sections mounted on... Use: The instrument will be used to examine portions of vertebrate and invertebrate organisms embedded...
Janson, Natalia B; Marsden, Christopher J
2017-12-05
It is well known that architecturally the brain is a neural network, i.e. a collection of many relatively simple units coupled flexibly. However, it has been unclear how the possession of this architecture enables higher-level cognitive functions, which are unique to the brain. Here, we consider the brain from the viewpoint of dynamical systems theory and hypothesize that the unique feature of the brain, the self-organized plasticity of its architecture, could represent the means of enabling the self-organized plasticity of its velocity vector field. We propose that, conceptually, the principle of cognition could amount to the existence of appropriate rules governing self-organization of the velocity field of a dynamical system with an appropriate account of stimuli. To support this hypothesis, we propose a simple non-neuromorphic mathematical model with a plastic self-organized velocity field, which has no prototype in physical world. This system is shown to be capable of basic cognition, which is illustrated numerically and with musical data. Our conceptual model could provide an additional insight into the working principles of the brain. Moreover, hardware implementations of plastic velocity fields self-organizing according to various rules could pave the way to creating artificial intelligence of a novel type.
Moon, Hong Chul; Lodge, Timothy P; Frisbie, C Daniel
2014-03-05
Ion gels comprising ABA triblock copolymers and ionic liquids have received much attention as functional materials in numerous applications, especially as gate dielectrics in organic transistors. Here we have expanded the functionality of ion gels by demonstrating low-voltage, flexible electrochemiluminescent (ECL) devices using patterned ion gels containing redox-active luminophores. The ECL devices consisted only of a 30 μm thick emissive gel and two electrodes and were fabricated on indium tin oxide-coated substrates (e.g., polyester) simply by solution-casting the ECL gel and brush-painting a top Ag electrode. The triblock copolymer employed in the gel was polystyrene-block-poly(methyl methacrylate)-block-polystyrene, where the solvophobic polystyrene end blocks associate into micellar cross-links in the versatile ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMI][TFSI]). An ECL gel containing ~6.25 wt % Ru(bpy)3Cl2 (relative to [EMI][TFSI]) as the luminophore turned on at an AC peak-to-peak voltage as low as 2.6 V (i.e., -1.3 to +1.3 V) and showed a relatively rapid response (sub-ms). The wavelength of maximum emission was 610 nm (red-orange). With the use of an iridium(III) complex, Ir(diFppy)2(bpy)PF6 [diFppy = 2-(2',4'-difluorophenyl)pyridine; bpy = 2,2'-bipyridyl], the emitting color was tuned to a maximum wavelength of 540 nm (green). Moreover, when a blended luminophore system containing a 60:40 mixture of Ru(bpy)3(2+) and Ir(diFppy)2(bpy)(+) was used in the emissive layer, the luminance of red-orange-colored light was enhanced by a factor of 2, which is explained by the generation of the additional excited state Ru(bpy)3(2+)* by a coreactant pathway with Ir(diFppy)2(bpy)(+)* in addition to the usual annihilation pathway. This is the first time that enhanced ECL has been achieved in ion gels (or ionic liquids) using a coreactant. Overall, the results indicate that ECL ion gels are attractive multifunctional materials for printed electronics.
NASA Astrophysics Data System (ADS)
Nakagawa, Hiroe; Fujino, Yukiko; Kozono, Suguru; Katayama, Yoshihiro; Nukuda, Toshiyuki; Sakaebe, Hikari; Matsumoto, Hajime; Tatsumi, Kuniaki
A mixture of flammable organic solvent and nonflammable room temperature ionic liquid (RTIL) has been investigated as a new concept electrolyte to improve the safety of lithium-ion cells. This study focused on the use of N-methyl- N-propylpiperidinium bis (trifluoromethanesulfonyl) imide (PP13-TFSI) as the RTIL for the flame-retardant additive. It was found that a carbon negative electrode, both graphite and hard carbon, could be used with the mixed electrolyte. A 383562-size lithium-ion trial cell made with the mixed electrolyte showed good discharge capacity, which was equivalent to a cell with conventional organic electrolyte up to a discharge current rate of complete discharge in 1 h. Moreover, the mixed electrolyte was observed to be nonflammable at ionic liquid contents of 40 mass% or more. Thus the mixed electrolyte was found to realize both nonflammability and the good discharge performance of lithium-ion cells with carbon negative electrodes. These results indicate that RTILs have potential as a flame-retardant additive for the organic electrolytes used in lithium-ion cells.
Radošević, Kristina; Železnjak, Jelena; Cvjetko Bubalo, Marina; Radojčić Redovniković, Ivana; Slivac, Igor; Gaurina Srček, Višnja
2016-09-01
With the advent of ionic liquids, much was expected concerning their applicability as an alternative to organic solvents in the chemical technology and biotechnology fields. However, the most studied and commonly used ionic liquids based on imidazolium and pyridinium were found not to be as environmentally friendly as it was first expected. Therefore, a new generation of alternative solvents named natural ionic liquids and deep eutectic solvents, composed of natural and/or renewable compounds, have come into focus in recent years. Since the number of newly synthesized chemicals increases yearly, simple and reliable methods for their ecotoxicological assessment are necessary. Permanent fish cell lines can serve as a test system for the evaluation of a chemical's cytotoxicity. This paper presents research results on the cytotoxic effects on Channel Catfish Ovary (CCO) cell line induced by fifteen cholinium-based ionic liquids and deep eutectic solvents. Based on the decrease in cell viability, the most obvious toxic effect on CCO cells was caused by ionic liquid choline oxalate, while other solvents tested exhibited low cytotoxicity. Therefore, we can conclude that cholinium-based ionic liquids and deep eutectic solvents are comparatively less toxic to CCO cells than conventional ionic liquids. Copyright © 2016 Elsevier Inc. All rights reserved.
40 CFR 52.777 - Control strategy: photochemical oxidants (hydrocarbons).
Code of Federal Regulations, 2014 CFR
2014-07-01
... plastics, automotive plastics, and synthetic organic chemical manufacturing industries (SOCMI) batch... wastewater processes, offset lithography operations, business plastics, automotive plastics, and synthetic... order between U.S. Steel (currently USX Corporation) and the IDEM signed by IDEM on March 22, 1996...
40 CFR 52.777 - Control strategy: photochemical oxidants (hydrocarbons).
Code of Federal Regulations, 2010 CFR
2010-07-01
... plastics, automotive plastics, and synthetic organic chemical manufacturing industries (SOCMI) batch... wastewater processes, offset lithography operations, business plastics, automotive plastics, and synthetic... order between U.S. Steel (currently USX Corporation) and the IDEM signed by IDEM on March 22, 1996...
40 CFR 52.777 - Control strategy: photochemical oxidants (hydrocarbons).
Code of Federal Regulations, 2011 CFR
2011-07-01
... plastics, automotive plastics, and synthetic organic chemical manufacturing industries (SOCMI) batch... wastewater processes, offset lithography operations, business plastics, automotive plastics, and synthetic... order between U.S. Steel (currently USX Corporation) and the IDEM signed by IDEM on March 22, 1996...
Sakamoto, Takeshi; Ogawa, Takafumi; Nada, Hiroki; Nakatsuji, Koji; Mitani, Masato; Soberats, Bartolome; Kawata, Ken; Yoshio, Masafumi; Tomioka, Hiroki; Sasaki, Takao; Kimura, Masahiro; Henmi, Masahiro; Kato, Takashi
2018-01-01
Supply of safe fresh water is currently one of the most important global issues. Membranes technologies are essential to treat water efficiently with low costs and energy consumption. Here, the development of self-organized nanostructured water treatment membranes based on ionic liquid crystals composed of ammonium, imidazolium, and pyridinium moieties is reported. Membranes with preserved 1D or 3D self-organized sub-nanopores are obtained by photopolymerization of ionic columnar or bicontinuous cubic liquid crystals. These membranes show salt rejection ability, ion selectivity, and excellent water permeability. The relationships between the structures and the transport properties of water molecules and ionic solutes in the sub-nanopores in the membranes are examined by molecular dynamics simulations. The results suggest that the volume of vacant space in the nanochannel greatly affects the water and ion permeability.
Ogawa, Takafumi; Nakatsuji, Koji; Mitani, Masato; Soberats, Bartolome; Kawata, Ken; Yoshio, Masafumi; Tomioka, Hiroki; Sasaki, Takao; Kimura, Masahiro
2017-01-01
Abstract Supply of safe fresh water is currently one of the most important global issues. Membranes technologies are essential to treat water efficiently with low costs and energy consumption. Here, the development of self‐organized nanostructured water treatment membranes based on ionic liquid crystals composed of ammonium, imidazolium, and pyridinium moieties is reported. Membranes with preserved 1D or 3D self‐organized sub‐nanopores are obtained by photopolymerization of ionic columnar or bicontinuous cubic liquid crystals. These membranes show salt rejection ability, ion selectivity, and excellent water permeability. The relationships between the structures and the transport properties of water molecules and ionic solutes in the sub‐nanopores in the membranes are examined by molecular dynamics simulations. The results suggest that the volume of vacant space in the nanochannel greatly affects the water and ion permeability. PMID:29375969
Three-dimensional biocompatible matrix for reconstructive surgery
NASA Astrophysics Data System (ADS)
Reshetov, I. V.; Starceva, O. I.; Istranov, A. L.; Vorona, B. N.; Lyundup, A. V.; Gulyaev, I. V.; Melnikov, D. V.; Shtansky, D. V.; Sheveyko, A. N.; Andreev, V. A.
2016-08-01
A study into the development of an original bioengineered structure for reconstruction of hollow organs is presented. The basis for the structure was the creation of a mesh matrix made from titanium nickelide (NiTi), which has sufficient elasticity and shape memory for the reconstruction of hollow tubular orgrans. In order to increase the cell adhesion on the surface of the matrix, the grid needed to be cleaned of impurities, for which we used an ionic cleaning method. Additional advantages also may enable the application of the bioactive component to grid surface. These features of the matrix may improve the biocompatibility properties of the composite material. In the first stage, a mesh structure was made from NiTi fibers. The properties of the resulting mesh matrix were studied. In the second stage, the degrees of adhesion and cell growth rates in the untreated matrix, the matrix after ionic cleaning and the matrix after ionic cleaning and the application of the bioactive component were compared. The results showed more significant biocompatibility of the titanium nickelide matrix after its ionic cleaning. The ionic cleaning ensures the removal of toxic contaminants, which are a consequence of the technological production process of the material and provide optimal adhesion properties for the fiber surface. The NiTi net matrix with TiCaPCON coating may be the optimal basis for making the hollow elastic organs.
Bui, Tung Xuan; Choi, Heechul
2010-08-01
The adsorption of four wide-use pharmaceuticals (carbamazepine, diclofenac, ibuprofen, and ketoprofen) onto a porous silica was investigated under varied ionic strengths, different anions, divalent cations (Ca(2+) and Mg(2+)), trivalent cations (Al(3+) and Fe(3+)), and natural organic matter (NOM). The experiments demonstrated that at a given pH the adsorption was most affected by ionic strength, trivalent cations, and properties of pharmaceuticals. The increase of ionic strength resulted in an increase in the adsorption of ketoprofen, but a decrease in the adsorption of carbamazepine. Trivalent metal cations made intense increases in the adsorption of three acidic pharmaceuticals, which could be due to the formation of inner-sphere complex of the cations on the surface and/or complexation of the pharmaceuticals with both surface and aqueous metal species. It was found that the adsorption of carbamazepine was not affected by divalent and trivalent cations, whereas the adsorption of diclofenac was solely impacted by the presence of Al(3+). Moreover, divalent cations at low concentration could slightly enhance the adsorption of ibuprofen and ketoprofen, whereas NOM caused a reduction in the adsorption of the tested pharmaceuticals except for diclofenac. These results suggest that ionic strength, divalent cations, trivalent cations, and NOM are notable factors affecting the adsorption of pharmaceuticals and thus the ultimate fate of pharmaceuticals in the aqueous environment. Copyright 2010 Elsevier Ltd. All rights reserved.
Search of non-ionic surfactants suitable for micellar liquid chromatography.
Peris-García, Ester; Rodríguez-Martínez, Jorge; Baeza-Baeza, Juan J; García-Alvarez-Coque, María Celia; Ruiz-Angel, María José
2018-06-19
Most reports in reversed-phase liquid chromatography (RPLC) with micellar mobile phases make use of the anionic sodium dodecyl sulfate. This surfactant masks efficiently the silanol groups that are the origin of the poor efficiencies and tailing peaks observed for basic compounds in conventional RPLC. However, it has the handicap of yielding excessive retention, which forces the addition of an organic solvent to reduce the retention times to practical values. Other surfactants, such as the non-ionic polyoxyethylene(23)lauryl ether (Brij-35), are rarely used. Brij-35 allows the separation of a large range of analytes in adequate retention times, without the need of adding an organic solvent to the mobile phase. However, this non-ionic surfactant shows irreversible adsorption on chromatographic columns and peak shape is poorer. Therefore, the search of non-ionic surfactants with similar properties to Brij-35, but showing reversible adsorption and better peak shape, can be of great interest. In this work, the adequacy of several non-ionic surfactants as modifiers in RPLC has been explored, being polyoxyethylene(10)tridecyl ether particularly attractive. The separation of different types of compounds was checked: sulfonamides (acidic), β-adrenoceptor antagonists and tricyclic antidepressants (basic with diverse polarity), and flavonoids (with and without hydroxyl groups on the aromatic rings). The chromatographic behaviors were examined in terms of retention and peak shape. The results were compared with those obtained with Brij-35.
Extraction of Organochlorine Pesticides from Plastic Pellets and Plastic Type Analysis.
Pflieger, Marilyne; Makorič, Petra; Kovač Viršek, Manca; Koren, Špela
2017-07-01
Plastic resin pellets, categorized as microplastics (≤5 mm in diameter), are small granules that can be unintentionally released to the environment during manufacturing and transport. Because of their environmental persistence, they are widely distributed in the oceans and on beaches all over the world. They can act as a vector of potentially toxic organic compounds (e.g., polychlorinated biphenyls) and might consequently negatively affect marine organisms. Their possible impacts along the food chain are not yet well understood. In order to assess the hazards associated with the occurrence of plastic pellets in the marine environment, it is necessary to develop methodologies that allow for rapid determination of associated organic contaminant levels. The present protocol describes the different steps required for sampling resin pellets, analyzing adsorbed organochlorine pesticides (OCPs) and identifying the plastic type. The focus is on the extraction of OCPs from plastic pellets by means of a pressurized fluid extractor (PFE) and on the polymer chemical analysis applying Fourier Transform-InfraRed (FT-IR) spectroscopy. The developed methodology focuses on 11 OCPs and related compounds, including dichlorodiphenyltrichloroethane (DDT) and its two main metabolites, lindane and two production isomers, as well as the two biologically active isomers of technical endosulfan. This protocol constitutes a simple and rapid alternative to existing methodology for evaluating the concentration of organic contaminants adsorbed on plastic pieces.
Plasticity of ductile metallic glasses: a self-organized critical state.
Sun, B A; Yu, H B; Jiao, W; Bai, H Y; Zhao, D Q; Wang, W H
2010-07-16
We report a close correlation between the dynamic behavior of serrated flow and the plasticity in metallic glasses (MGs) and show that the plastic deformation of ductile MGs can evolve into a self-organized critical state characterized by the power-law distribution of shear avalanches. A stick-slip model considering the interaction of multiple shear bands is presented to reveal complex scale-free intermittent shear-band motions in ductile MGs and quantitatively reproduce the experimental observations. Our studies have implications for understanding the precise plastic deformation mechanism of MGs.
Endocrine regulation of predator-induced phenotypic plasticity.
Dennis, Stuart R; LeBlanc, Gerald A; Beckerman, Andrew P
2014-11-01
Elucidating the developmental and genetic control of phenotypic plasticity remains a central agenda in evolutionary ecology. Here, we investigate the physiological regulation of phenotypic plasticity induced by another organism, specifically predator-induced phenotypic plasticity in the model ecological and evolutionary organism Daphnia pulex. Our research centres on using molecular tools to test among alternative mechanisms of developmental control tied to hormone titres, receptors and their timing in the life cycle. First, we synthesize detail about predator-induced defenses and the physiological regulation of arthropod somatic growth and morphology, leading to a clear prediction that morphological defences are regulated by juvenile hormone and life-history plasticity by ecdysone and juvenile hormone. We then show how a small network of genes can differentiate phenotype expression between the two primary developmental control pathways in arthropods: juvenoid and ecdysteroid hormone signalling. Then, by applying an experimental gradient of predation risk, we show dose-dependent gene expression linking predator-induced plasticity to the juvenoid hormone pathway. Our data support three conclusions: (1) the juvenoid signalling pathway regulates predator-induced phenotypic plasticity; (2) the hormone titre (ligand), rather than receptor, regulates predator-induced developmental plasticity; (3) evolution has favoured the harnessing of a major, highly conserved endocrine pathway in arthropod development to regulate the response to cues about changing environments (risk) from another organism (predator).
Ionic liquids as an electrolyte for the electro synthesis of organic compounds.
Kathiresan, Murugavel; Velayutham, David
2015-12-25
The use of ionic liquids (ILs) as a solvent and an electrolyte for electro organic synthesis has been reviewed. To date several ILs exist, however the ILs based on tetraalkylammonium, pyrrolidinium, piperidinium and imidazolium cations with BF4(-), PF6(-), and TFSI anions have been widely used and explored the most. Electro organic synthesis in ionic liquid media leading to the synthesis of a wide range of organic compounds has been discussed. Anodic oxidation or cathodic reduction will generate radical cation or anion intermediates, respectively. These radicals can undergo self coupling or coupling with other molecules yielding organic compounds of interest. The cation of the IL is known to stabilize the radical anion extensively. This stabilization effect has a specific impact on the electrochemical CO2 reduction and coupling to various organics. The relative stability of the intermediates in IL leads to the formation of specific products in higher yields. Electrochemical reduction of imidazolium or thiazolium based ILs generates N-heterocyclic carbenes that have been shown to catalyze a wide range of base or nucleophile catalyzed organic reactions in IL media, an aspect that falls into the category of organocatalysis. Electrochemical fluorination or selective electrochemical fluorination is another fascinating area that delivers selectively fluorinated organic products in Et3N·nHF or Et4NF·nHF adducts (IL) via anodic oxidation. Oxidative polymerization in ILs has been explored the most; although morphological changes were observed compared to the conventional methods, polymers were obtained in good yields and in some cases ILs were used as dopants to improve the desired properties.
NASA Astrophysics Data System (ADS)
Shekaari, Hemayat; Zafarani-Moattar, Mohammed Taghi
2008-04-01
Apparent molar volumes, V_φ , and compressibilities, kappa _φ , of 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF4]) have been determined from precise density and speed-of-sound measurements in organic solvents, methanol (MeOH), acetonitrile (MeCN), tetrahydrofuran (THF), N, N-dimethylacetamide (DMA), and dimethylsulfoxide (DMSO) in the dilute region of the ionic liquid. Corresponding values at infinite dilution are estimated by the Redlich-Mayer and Pitzer equations. The results have been interpreted by the interaction of the [BMIm][BF4] in the organic solvents. Results show that the structure and dielectric constant of the organic solvents play an important role for the ion-solvent interactions in these mixtures. It was found that the strength of interaction between [BMIm][BF4] with the studied organic solvents has the order DMSO > DMA > MeOH > MeCN > THF.
Constraints on the evolution of phenotypic plasticity: limits and costs of phenotype and plasticity
Murren, C J; Auld, J R; Callahan, H; Ghalambor, C K; Handelsman, C A; Heskel, M A; Kingsolver, J G; Maclean, H J; Masel, J; Maughan, H; Pfennig, D W; Relyea, R A; Seiter, S; Snell-Rood, E; Steiner, U K; Schlichting, C D
2015-01-01
Phenotypic plasticity is ubiquitous and generally regarded as a key mechanism for enabling organisms to survive in the face of environmental change. Because no organism is infinitely or ideally plastic, theory suggests that there must be limits (for example, the lack of ability to produce an optimal trait) to the evolution of phenotypic plasticity, or that plasticity may have inherent significant costs. Yet numerous experimental studies have not detected widespread costs. Explicitly differentiating plasticity costs from phenotype costs, we re-evaluate fundamental questions of the limits to the evolution of plasticity and of generalists vs specialists. We advocate for the view that relaxed selection and variable selection intensities are likely more important constraints to the evolution of plasticity than the costs of plasticity. Some forms of plasticity, such as learning, may be inherently costly. In addition, we examine opportunities to offset costs of phenotypes through ontogeny, amelioration of phenotypic costs across environments, and the condition-dependent hypothesis. We propose avenues of further inquiry in the limits of plasticity using new and classic methods of ecological parameterization, phylogenetics and omics in the context of answering questions on the constraints of plasticity. Given plasticity's key role in coping with environmental change, approaches spanning the spectrum from applied to basic will greatly enrich our understanding of the evolution of plasticity and resolve our understanding of limits. PMID:25690179
A method has been developed to measure the swelling properties of Concentrated natural organic materials in various organic liquids, and has been applied to various eat, pollen, chitin and cellulose samples. The swelling of these macromolecular aterials is rhe volumetric manifest...
A method has been developed to measure the swelling properties of Concentrated natural organic materials in various organic liquids, and has been applied to various eat, pollen, chitin and cellulose samples. he swelling of these macromolecular aterials is rhe volumetric manifesta...
Novel Elastomeric Membranes Developed for Polymer Electrolytes in Lithium Batteries
NASA Technical Reports Server (NTRS)
Tigelaar, Dean M.; Meador, Maryann B.; Kinder, James D.; Bennett, William R.
2005-01-01
Lithium-based polymer batteries for aerospace applications need to be highly conductive from -70 to 70 C. State-of-the-art polymer electrolytes are based on polyethylene oxide (PEO) because of the ability of its ether linkages to solvate lithium ions. Unfortunately, PEO has a tendency to form crystalline regions below 60 C, dramatically lowering conductivity below this temperature. PEO has acceptable ionic conductivities (10(exp -4) to 10(exp -3) S/cm) above 60 C, but it is not mechanically strong. The room-temperature conductivity of PEO can be increased by adding solvent or plasticizers, but this comes at the expense of thermal and mechanical stability. One of NASA Glenn Research Center s objectives in the Polymer Rechargeable System program (PERS) is to develop novel polymer electrolytes that are highly conductive at and below room temperature without added solvents or plasticizers.
Akaighe, Nelson; Depner, Sean W; Banerjee, Sarbajit; Sohn, Mary
2013-07-01
The transport and deposition of silver nanoparticles (AgNPs) formed from Ag(+) reduction by Suwannee River Humic Acid (SRHA) and Suwannee River Natural Organic Matter (SRNOM) utilizing a silica matrix is reported. The morphology and stability of the AgNPs was analyzed by transmission electron microscopy (TEM), dynamic light scattering (DLS) and zeta potential measurements. The percentage conversion of the initial [Ag(+)] to [AgNPs] was determined from a combination of atomic absorption (AAS) and UV-Vis spectroscopy, and centrifugation techniques. The results indicate higher AgNP transport and consequently low deposition in the porous media at basic pH conditions and low ionic strength. However, at low acidic pH and high ionic strength, especially with the divalent metallic cations, the mobility of the AgNPs in the porous media was very low, most likely due to NP aggregation. Overall, the results suggest the potential for AgNP contamination of subsurface soils and groundwater aquifers is mostly dependent on their aggregation state, controlled by the soil water and sediment ionic strength and pH. Copyright © 2013 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Lo Celso, F.; Appetecchi, G. B.; Jafta, C. J.; Gontrani, L.; Canongia Lopes, J. N.; Triolo, A.; Russina, O.
2018-05-01
Fluorinated Room Temperature Ionic Liquids (FRTILs) are a branch of ionic liquids that is the object of growing interest for a wide range of potential applications, due to the synergic combination of specifically ionic features and those properties that stem from fluorous tails. So far limited experimental work exists on the micro- and mesoscopic structural organization in this class of compounds. Such a work is however necessary to fully understand morphological details at atomistic level that would have strong implications in terms of bulk properties. Here we use the synergy between X-ray and neutron scattering together with molecular dynamics simulations to access structural details of a technologically relevant FRTIL that is characterised by an anion bearing a long enough fluorinated tail to develop specific morphological features. In particular, we find the first experimental evidence that in FRTILs bearing an asymmetric bis(perfluoroalkyl)sulfonyl-imide anion, fluorous side chains tend to be spatially segregated into nm-scale spatial heterogeneities. This feature together with the well-established micro-segregation of side alkyl chains in conventional RTILs leads to the concept of triphilic ILs, whose technological applications are yet to be fully developed.
NASA Astrophysics Data System (ADS)
Jing, Benxin; Lan, Nan; Zhu, Y. Elaine
2013-03-01
An explosion in the research activities using ionic liquids (ILs) as new ``green'' chemicals in several chemical and biomedical processes has resulted in the urgent need to understand their impact in term of their transport and toxicity towards aquatic organisms. Though a few experimental toxicology studies have reported that some ionic liquids are toxic with increased hydrophobicity of ILs while others are not, our understanding of the molecular level mechanism of IL toxicity remains poorly understood. In this talk, we will discuss our recent study of the interaction of ionic liquids with model cell membranes. We have found that the ILs could induce morphological change of lipid bilayers when a critical concentration is exceeded, leading to the swelling and tube-like formation of lipid bilayers. The critical concentration shows a strong dependence on the length of hydrocarbon tails and hydrophobic counterions. By SAXS, Langmuir-Blodgett (LB) and fluorescence microscopic measurement, we have confirmed that tube-like lipid complexes result from the insertion of ILs with long hydrocarbon chains to minimize the hydrophobic interaction with aqueous media. This finding could give insight to the modification and adoption of ILs for the engineering of micro-organisms.
Banerjee, Abhinandan; Theron, Robin; Scott, Robert W J
2012-01-09
Gold and palladium nanoparticles were prepared by lithium borohydride reduction of the metal salt precursors in tetraalkylphosphonium halide ionic liquids in the absence of any organic solvents or external nanoparticle stabilizers. These colloidal suspensions remained stable and showed no nanoparticle agglomeration over many months. A combination of electrostatic interactions between the coordinatively unsaturated metal nanoparticle surface and the ionic-liquid anions, bolstered by steric protection offered by the bulky alkylated phosphonium cations, is likely to be the reason behind such stabilization. The halide anion strongly absorbs to the nanoparticle surface, leading to exceptional nanoparticle stability in halide ionic liquids; other tetraalkylphosphonium ionic liquids with non-coordinating anions, such as tosylate and hexafluorophosphate, show considerably lower affinities towards the stabilization of nanoparticles. Palladium nanoparticles stabilized in the tetraalkylphosphonium halide ionic liquid were stable, efficient, and recyclable catalysts for a variety of hydrogenation reactions at ambient pressures with sustained activity. Aerial oxidation of the metal nanoparticles occurred over time and was readily reversed by re-reduction of oxidized metal salts. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Andersen, Stephen J; Berton, Jan K E T; Naert, Pieter; Gildemyn, Sylvia; Rabaey, Korneel; Stevens, Christian V
2016-08-23
Ionic liquids can both act as a solvent and mediate esterification to valorize low-titer volatile fatty acids and generate organic solvents from renewable carbon sources including biowaste and CO2 . In this study, four phosphonium ionic liquids were tested for single-stage extraction of acetic acid from a dilute stream and esterification to ethyl acetate with added ethanol and heat. The esterification proceeded with a maximum conversion of 85.9±1.3 % after 30 min at 75 °C at a 1:1 stoichiometric ratio of reactants. Extraction and esterification can be tailored using mixed-anion ionic liquids; this is demonstrated herein using a common trihexyl(tetradecyl)phosphonium cation and a mixed chloride and bis(trifluoromethylsulfonyl)imide anion ionic liquid. As a further proof-of-concept, ethyl acetate was generated from an ionic liquid-driven esterification of an acetic acid extractant generated using CO2 as the only carbon source by microbial electrosynthesis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Lee, Hwang; Byun, Da-Eun; Kim, Ju Min; Kwon, Jung-Hwan
2018-01-01
To evaluate rate of migration from plastic debris, desorption of model hydrophobic organic chemicals (HOCs) from polyethylene (PE)/polypropylene (PP) films to water was measured using PE/PP films homogeneously loaded with the HOCs. The HOCs fractions remaining in the PE/PP films were compared with those predicted using a model characterized by the mass transfer Biot number. The experimental data agreed with the model simulation, indicating that HOCs desorption from plastic particles can generally be described by the model. For hexachlorocyclohexanes with lower plastic-water partition coefficients, desorption was dominated by diffusion in the plastic film, whereas desorption of chlorinated benzenes with higher partition coefficients was determined by diffusion in the aqueous boundary layer. Evaluation of the fraction of HOCs remaining in plastic films with respect to film thickness and desorption time showed that the partition coefficient between plastic and water is the most important parameter influencing the desorption half-life. Copyright © 2017 Elsevier Ltd. All rights reserved.
Kim, Gahee; Hong, Lan Young; Jung, Jungwoon; Kim, Dong-Pyo; Kim, Heesoo; Kim, Ik Jung; Kim, Jung Ran; Ree, Moonhor
2010-03-01
New mesoporous silicate-titania resin systems hybridized with 4,5-dihydroxy-m-benzenedisulfonic acid and poly(ethylene glycol)-dimethacrylate component were developed. These inorganic-organic hybrid resins were found to reveal highly controlled ionic and hydrophilic surface with excellent durability and adhesion onto various substrates. The resin films revealed high resistance to nonspecific adsorption of fibrinogen and to adherence by several bacterial pathogens such as Escherichia coli, Staphylococcus aureus, Staphylococcus epidermidis and Enterococcus faecalis. Furthermore, excellent biocompatibility of the developed resins was proved by both HEp-2 cell adhesion in vitro and subcutaneous implantation in mice. The inorganic-organic hybrid resins are strongly promising for biomedical applications including biomedical devices and biosensors. Copyright 2009 Elsevier Ltd. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Castillo, M.; Alonso, M.C.; Riu, J.
1999-04-15
This paper presents a generic protocol for the determination of polar, ionic, and highly water soluble organic pollutants on untreated industrial wastewaters involving the use of two different solid-phase extraction (SPE) methodologies followed by liquid chromatography-mass spectrometry (LC-MS). Untreated industrial wastewaters might contain natural and synthetic dissolved organic compounds with total organic carbon (TOC) values varying between 100 and 3000 mg/L. All polar, ionic and highly water soluble compounds comprising more than 95% of the organic content and with major contribution to the total toxicity of the sample cannot be analyzed by conventional gas chromatography-mass spectrometry (GC-MS), and LC-MS ismore » a good alternative. In this work two extraction procedures were used to obtain fractionated extracts of the nonionic polar compounds: a polymeric Isolute ENV + SPE cartridge for the preconcentration of anionic analytes and a sequential solid-phase extraction (SSPE) method percolating the samples first in octadecylsilica cartridge in series with the polymeric Lichrolut EN cartridge. Average recoveries ranging from 72% to 103% were obtained for a variety of 23 different analytes. Determination of nonionic pollutants was accomplished by reverse-phase liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry (LC-APCI-MS), while anionic compounds were analyzed by ion pair chromatography-electrospray-mass spectrometry (IP-ESI-MS) and LC-ESI-MS. This protocol was applied to a pilot survey of textile and tannery wastewaters leading to the identification and quantification of 33 organic pollutants.« less
Li, Heng-Xiang; Orihuela, Beatriz; Zhu, Mei; Rittschof, Daniel
2016-11-01
Plastics are common and pervasive anthropogenic debris in marine environments. Floating plastics provide opportunities to alter the abundance, distribution and invasion potential of sessile organisms that colonize them. We selected plastics from seven recycle categories and quantified settlement of (i) bryozoans Bugula neritina (Linnaeus, 1758) in the lab and in the field, and of (ii) barnacles Amphibalanus (= Balanus) amphitrite (Darwin, 1854) in the field. In the laboratory we cultured barnacles on the plastics for 8 weeks and quantified growth, mortality, and breaking strength of the side plates. In the field all recyclable plastics were settlement substrata for bryozoans and barnacles. Settlement depended on the type of plastic. Fewer barnacles settled on plastic surfaces compared to glass. In the lab and in the field, bryozoan settlement was higher on plastics than on glass. In static laboratory rearing, barnacles growing on plastics were initially significantly smaller than on glass. This suggested juvenile barnacles were adversely impacted by materials leaching from the plastics. Barnacle mortality was not significantly different between plastic and glass surfaces, but breaking strength of side plates of barnacles on polyvinyl chloride (PVC) and polycarbonate (PC) were significantly lower than breakage strength on glass. Plastics impact marine ecosystems directly by providing new surfaces for colonization with fouling organisms and by contaminants shown previously to leach out of plastics and impact biological processes. Published by Elsevier Ltd.
Nilsson, Martin; Frenning, Göran; Gråsjö, Johan; Alderborn, Göran; Strømme, Maria
2006-10-19
The present study aims at contributing to a complete understanding of the water-induced ionic charge transport in cellulose. The behavior of this transport in loosely compacted microcrystalline cellulose (MCC) powder was investigated as a function of density utilizing a new type of measurement setup, allowing for dielectric spectroscopy measurement in situ during compaction. The ionic conductivity in MCC was found to increase with increasing density until a leveling-out was observed for densities above approximately 0.7 g/cm3. Further, it was shown that the ionic conductivity vs density followed a percolation type behavior signifying the percolation of conductive paths in a 3D conducting network. The density percolation threshold was found to be between approximately 0.2 and 0.4 g/cm3, depending strongly on the cellulose moisture content. The observed percolation behavior was attributed to the forming of interparticulate bonds in the MCC and the percolation threshold dependence on moisture was linked to the moisture dependence of particle rearrangement and plastic deformation in MCC during compaction. The obtained results add to the understanding of the density-dependent water-induced ionic transport in cellulose showing that, at given moisture content, the two major parameters determining the magnitude of the conductivity are the connectedness of the interparticluate bonds and the connectedness of pores with a diameter in the 5-20 nm size range. At densities between approximately 0.7 and 1.2 g/cm3 both the bond and the pore networks have percolated, facilitating charge transport through the MCC compact.
The chemical structure of plastics greatly differs from natural marine particulate matter and therefore plastics likely are creating new and unique niches for microorganisms in the ocean. It is hypothesized that the microbes found on plastic particles will be taxonomically ...
Pang, JinHui; Wu, Miao; Zhang, QiaoHui; Tan, Xin; Xu, Feng; Zhang, XueMing; Sun, RunCang
2015-05-05
With the serious "white pollution" resulted from the non-biodegradable plastic films, considerable attention has been directed toward the development of renewable and biodegradable cellulose-based film materials as substitutes of petroleum-derived materials. In this study, environmentally friendly cellulose films were successfully prepared using different celluloses (pine, cotton, bamboo, MCC) as raw materials and ionic liquid 1-ethyl-3-methylimidazolium acetate as a solvent. The SEM and AFM indicated that all cellulose films displayed a homogeneous and smooth surface. In addition, the FT-IR and XRD analysis showed the transition from cellulose I to II was occurred after the dissolution and regeneration process. Furthermore, the cellulose films prepared by cotton linters and pine possessed the most excellent thermal stability and mechanical properties, which were suggested by the highest onset temperature (285°C) and tensile stress (120 MPa), respectively. Their excellent properties of regenerated cellulose films are promising for applications in food packaging and medical materials. Copyright © 2014 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Krief, Menahem; Kurzweil, Yair; Feigel, Alexander; Gazit, Doron
2018-04-01
With the aim of solving the decade-old problem of solar opacity, we report substantial photoabsorption uncertainty due to the effect of ion–ion correlations. By performing detailed opacity calculations of the solar mixture, we find that taking into account the ionic structure changes the Rosseland opacity near the convection zone by ∼10%. We also report a ∼15% difference in the Rosseland opacity for iron, which was recently measured at the Sandia Z facility, where the temperature reached that prevailing in the convection zone boundary while the density was 2.5 times lower. Finally, we propose a method to measure opacities at solar temperatures and densities that have never been reached in the past via laboratory radiation flow experiments, by using plastic foams doped with permilles of dominant photon absorbers in the Sun. The method is advantageous for an experimental study of solar opacities that may lead to a resolution of the solar abundance problem.
Plastics in the Ocean: More Than a Litter Problem.
ERIC Educational Resources Information Center
Center for Environmental Education, Washington, DC.
Environmental impacts arise from entanglement of marine animals in plastic debris and from ingestion of plastics by marine organisms. Plastic debris can cause potential threats to humans when divers become entangled or vessels become fouled in debris. The depletion of fishery resources, vessel damage, and aesthetic degradation resulting in lost…
Porcar, Raúl; Nuevo, Daniel; García-Verdugo, Eduardo; Lozano, Pedro; Sanchez-Marcano, José; Burguete, M Isabel; Luis, Santiago V
2018-03-07
Porous monolithic advanced functional materials based on supported ionic liquid-like phase (SILLP) systems were used for the preparation of oleophilic and hydrophobic cylindrical membranes and successfully tested as eco-friendly and safe systems for oil/water separation and for the continuous integration of catalytic and separation processes in an aqueous-organic biphasic reaction system.
Aguilera-Herrador, Eva; Lucena, Rafael; Cárdenas, Soledad; Valcárcel, Miguel
2008-10-31
A simple, rapid, solventless method for the determination of trihalomethanes (THMs) (chloroform, bromodichloromethane, dibromochloromethane and bromoform) in water samples is presented. The analytes are extracted from the headspace of the aqueous matrix into a 2 microL drop of the ionic liquid 1-octyl-3-methyl-imidazolium hexafluorophosphate working at 30 degrees C for 30 min. The separation and detection of the target compounds is accomplished by gas chromatography/mass spectrometry owing to the use of an interface that efficiently transfers the analytes extracted in the ionic liquid drop to the gas chromatograph while preventing the ionic liquid from entering the column. The detection limits obtained are below the values compelled by the legislation, ranging from 0.5 microg L(-1) for chloroform and bromodichloromethane to 0.9 microg L(-1) for dibromochloromethane. The use of ionic liquid in the extraction procedure avoids the use of organic solvents and leads to relative standard deviations that range from 3.1% to 4.8%.
Influence of Nanosegregation on the Surface Tension of Fluorinated Ionic Liquids
Luís, Andreia; Shimizu, Karina; Araújo, João M. M.; Carvalho, Pedro J.; Lopes-da-Silva, José A.; Canongia Lopes, José N.; Rebelo, Luís Paulo N.; Coutinho, João A. P.; Freire, Mara G.; Pereiro, Ana B.
2017-01-01
We have investigated, both theoretically and experimentally, the balance between the presence of alkyl and perfluoroalkyl side chains on the surface organization and surface tension of fluorinated ionic liquids (FILs). A series of ILs composed of 1-alkyl-3-methylimidazolium cations ([CnC1im] with n = 2, 4, 6, 8, 10 or 12) combined with the perfluorobutanesulfonate anion was used. The surface tensions of the investigated liquid salts are considerably lower than those reported for non-fluorinated ionic liquids. The most surprising and striking feature was the identification, for the first time, of a minimum at n = 8 in the surface tension versus the length of the IL cation alkyl side chain. Supported by molecular dynamic simulations it was found that this trend is a result of the competition between the two nonpolar domains (perfluorinated and aliphatic) on pointing towards the gas-liquid interface, a phenomenon which occurs in ionic liquids with perfluorinated anions. Furthermore, these ionic liquids present the lowest surface entropy reported to date. PMID:27218210
NASA Astrophysics Data System (ADS)
Shinoda, Wataru; Hatanaka, Yuta; Hirakawa, Masashi; Okazaki, Susumu; Tsuzuki, Seiji; Ueno, Kazuhide; Watanabe, Masayoshi
2018-05-01
Equimolar mixtures of glymes and organic lithium salts are known to produce solvate ionic liquids, in which the stability of the [Li(glyme)]+ complex plays an important role in determining the ionic dynamics. Since these mixtures have attractive physicochemical properties for application as electrolytes, it is important to understand the dependence of the stability of the [Li(glyme)]+ complex on the ion dynamics. A series of microsecond molecular dynamics simulations has been conducted to investigate the dynamic properties of these solvate ionic liquids. Successful solvate ionic liquids with high stability of the [Li(glyme)]+ complex have been shown to have enhanced ion dynamics. Li-glyme pair exchange rarely occurs: its characteristic time is longer than that of ion diffusion by one or two orders of magnitude. Li-glyme pair exchange most likely occurs through cluster formation involving multiple [Li(glyme)]+ pairs. In this process, multiple exchanges likely take place in a concerted manner without the production of energetically unfavorable free glyme or free Li+ ions.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Boisvert, Annie; Jones, Steven; Issop, Leeyah
Plasticizers are indispensable additives providing flexibility and malleability to plastics. Among them, several phthalates, including di (2-ethylhexyl) phthalate (DEHP), have emerged as endocrine disruptors, leading to their restriction in consumer products and creating a need for new, safer plasticizers. The goal of this project was to use in vitro functional screening tools to select novel non-toxic plasticizers suitable for further in vivo evaluation. A panel of novel compounds with satisfactory plasticizer properties and biodegradability were tested, along with several commercial plasticizers, such as diisononyl-cyclohexane-1,2-dicarboxylate (DINCH®). MEHP, the monoester metabolite of DEHP was also included as reference compound. Because phthalates targetmore » mainly testicular function, including androgen production and spermatogenesis, we used the mouse MA-10 Leydig and C18-4 spermatogonial cell lines as surrogates to examine cell survival, proliferation, steroidogenesis and mitochondrial integrity. The most promising compounds were further assessed on organ cultures of rat fetal and neonatal testes, corresponding to sensitive developmental windows. Dose-response studies revealed the toxicity of most maleates and fumarates, while identifying several dibenzoate and succinate plasticizers as innocuous on Leydig and germ cells. Interestingly, DINCH®, a plasticizer marketed as a safe alternative to phthalates, exerted a biphasic effect on steroid production in MA-10 and fetal Leydig cells. MEHP was the only plasticizer inducing the formation of multinucleated germ cells (MNG) in organ culture. Overall, organ cultures corroborated the cell line data, identifying one dibenzoate and one succinate as the most promising candidates. The adoption of such collaborative approaches for developing new chemicals should help prevent the development of compounds potentially harmful to human health. - Highlights: • Phthalate plasticizers exert toxic effects on male reproduction. • Reproductive toxicity of new plasticizers was assessed by functional assays. • Mouse Leydig and germ cell lines, and rat perinatal testis cultures were used. • Survival, proliferation, steroidogenesis, abnormal germ cell formation were examined. • Reproductive toxic and innocuous plasticizer candidates were identified.« less
NASA Astrophysics Data System (ADS)
Lee, Joonseong; Kim, Seonghoon; Chang, Rakwoo; Jayanthi, Lakshmi; Gebremichael, Yeshitila
2013-01-01
The present study examines the effects of the model dependence, ionic strength, divalent ions, and hydrophobic interaction on the structural organization of the human neurofilament (NF) brush, using canonical ensemble Monte Carlo (MC) simulations of a coarse-grained model with the amino-acid resolution. The model simplifies the interactions between the NF core and the sidearm or between the sidearms by the sum of excluded volume, electrostatic, and hydrophobic interactions, where both monovalent salt ions and solvents are implicitly incorporated into the electrostatic interaction potential. Several important observations are made from the MC simulations of the coarse-grained model NF systems. First, the mean-field type description of monovalent salt ions works reasonably well in the NF system. Second, the manner by which the NF sidearms are arranged on the surface of the NF backbone core has little influence on the lateral extension of NF sidearms. Third, the lateral extension of the NF sidearms is highly affected by the ionic strength of the system: at low ionic strength, NF-M is most extended but at high ionic strength, NF-H is more stretched out because of the effective screening of the electrostatic interaction. Fourth, the presence of Ca2 + ions induces the attraction between negatively charged residues, which leads to the contraction of the overall NF extension. Finally, the introduction of hydrophobic interaction does not change the general structural organization of the NF sidearms except that the overall extension is contracted.
Linak, W P; Ryan, J V; Perry, E; Williams, R W; DeMarini, D M
1989-06-01
Chemical and biological analyses were performed to characterize products of incomplete combustion emitted during the simulated open field burning of agricultural plastic. A small utility shed equipped with an air delivery system was used to simulate pile burning and forced-air-curtain incineration of a nonhalogenated agricultural plastic that reportedly consisted of polyethylene and carbon black. Emissions were analyzed for combustion gases; volatile, semi-volatile, and particulate organics; and toxic and mutagenic properties. Emission samples, as well as samples of the used (possibly pesticide-contaminated) plastic, were analyzed for the presence of several pesticides to which the plastic may have been exposed. Although a variety of alkanes, alkenes, and aromatic and polycyclic aromatic hydrocarbon (PAH) compounds were identified in the volatile, semi-volatile, and particulate fractions of these emissions, a substantial fraction of higher molecular weight organic material was not identified. No pesticides were identified in either combustion emission samples or dichloromethane washes of the used plastic. When mutagenicity was evaluated by exposing Salmonella bacteria (Ames assay) to whole vapor and vapor/particulate emissions, no toxic or mutagenic effects were observed. However, organic extracts of the particulate samples were moderately mutagenic. This mutagenicity compares approximately to that measured from residential wood heating on a revertant per unit heat release basis. Compared to pile burning, forced air slightly decreased the time necessary to burn a charge of plastic. There was not a substantial difference, however, in the variety or concentrations of organic compounds identified in samples from these two burn conditions. This study highlights the benefits of a combined chemical/biological approach to the characterization of complex, multi-component combustion emissions. These results may not reflect those of other types of plastic that may be used for agricultural purposes, especially those containing halogens.
NASA Astrophysics Data System (ADS)
Li, Xiumin; Wang, Wei; Xue, Fangzheng; Song, Yongduan
2018-02-01
Recently there has been continuously increasing interest in building up computational models of spiking neural networks (SNN), such as the Liquid State Machine (LSM). The biologically inspired self-organized neural networks with neural plasticity can enhance the capability of computational performance, with the characteristic features of dynamical memory and recurrent connection cycles which distinguish them from the more widely used feedforward neural networks. Despite a variety of computational models for brain-like learning and information processing have been proposed, the modeling of self-organized neural networks with multi-neural plasticity is still an important open challenge. The main difficulties lie in the interplay among different forms of neural plasticity rules and understanding how structures and dynamics of neural networks shape the computational performance. In this paper, we propose a novel approach to develop the models of LSM with a biologically inspired self-organizing network based on two neural plasticity learning rules. The connectivity among excitatory neurons is adapted by spike-timing-dependent plasticity (STDP) learning; meanwhile, the degrees of neuronal excitability are regulated to maintain a moderate average activity level by another learning rule: intrinsic plasticity (IP). Our study shows that LSM with STDP+IP performs better than LSM with a random SNN or SNN obtained by STDP alone. The noticeable improvement with the proposed method is due to the better reflected competition among different neurons in the developed SNN model, as well as the more effectively encoded and processed relevant dynamic information with its learning and self-organizing mechanism. This result gives insights to the optimization of computational models of spiking neural networks with neural plasticity.
Theoretical and Numerical Modeling of faceted Ionic crystalline vesicles
NASA Astrophysics Data System (ADS)
Olvera de La Cruz, Monica
2007-03-01
Icosahedral shape is found in several natural structures including large viruses, large fullerenes and cationic-anionic vesicles. Faceting into icosahedral shape can occur in large crystalline membranes via elasticity theory. Icosahedral symmetry is found in small systems of particles with short-range interactions on a sphere. Dr G. Vernizzi and I show a novel electrostatic-driven mechanism of ionic crystalline shells faceting into icosahedral shapes even for systems with a small number of particles. Icosahedral shape is possible in cationic and anionic molecules adsorbed onto spherical interfaces, such as emulsions or other immiscible liquid droplets because the large concentration of charges at the interface can lead to ionic crystals on the curved interface. Such self-organized ionic structures favors the formation of flat surfaces. We find that these ionic crystalline shells can have lower energy when faceted into icosahedra along particular directions. Indeed, the ``ionic'' buckling is driven by preferred bending directions of the planar ionic structure, along which is more likely for the icosahedral shape to develop an edge. Since only certain orientations are allowed, rotational symmetry is broken. One can hope to exploit this mechanism to generate functional materials where, for instance, proteins with specific charge groups can orient at specific directions along an icosahedral cationic-anionic vesicle.
Method for Reduction of Silver Biocide Plating on Metal Surfaces
NASA Technical Reports Server (NTRS)
Steele, John; Nalette, Timothy; Beringer, Durwood
2013-01-01
Silver ions in aqueous solutions (0.05 to 1 ppm) are used for microbial control in water systems. The silver ions remain in solution when stored in plastic containers, but the concentration rapidly decreases to non-biocidal levels when stored in metal containers. The silver deposits onto the surface and is reduced to non-biocidal silver metal when it contacts less noble metal surfaces, including stainless steel, titanium, and nickel-based alloys. Five methods of treatment of contact metal surfaces to deter silver deposition and reduction are proposed: (1) High-temperature oxidation of the metal surface; (2) High-concentration silver solution pre-treatment; (3) Silver plating; (4) Teflon coat by vapor deposition (titanium only); and (5) A combination of methods (1) and (2), which proved to be the best method for the nickel-based alloy application. The mechanism associated with surface treatments (1), (2), and (5) is thought to be the development of a less active oxide layer that deters ionic silver deposition. Mechanism (3) is an attempt to develop an equilibrium ionic silver concentration via dissolution of metallic silver. Mechanism (4) provides a non-reactive barrier to deter ionic silver plating. Development testing has shown that ionic silver in aqueous solution was maintained at essentially the same level of addition (0.4 ppm) for up to 15 months with method (5) (a combination of methods (1) and (2)), before the test was discontinued for nickel-based alloys. Method (1) resulted in the maintenance of a biocidal level (approximately 0.05 ppm) for up to 10 months before that test was discontinued for nickel-based alloys. Methods (1) and (2) used separately were able to maintain ionic silver in aqueous solution at essentially the same level of addition (0.4 ppm) for up to 10 months before the test was discontinued for stainless steel alloys. Method (3) was only utilized for titanium alloys, and was successful at maintaining ionic silver in aqueous solution at essentially the same level of addition (0.4 ppm) for up to 10 months before the test was discontinued for simple flat geometries, but not for geometries that are difficult to Teflon coat.
John, Rohit Abraham; Liu, Fucai; Chien, Nguyen Anh; Kulkarni, Mohit R; Zhu, Chao; Fu, Qundong; Basu, Arindam; Liu, Zheng; Mathews, Nripan
2018-06-01
Emulation of brain-like signal processing with thin-film devices can lay the foundation for building artificially intelligent learning circuitry in future. Encompassing higher functionalities into single artificial neural elements will allow the development of robust neuromorphic circuitry emulating biological adaptation mechanisms with drastically lesser neural elements, mitigating strict process challenges and high circuit density requirements necessary to match the computational complexity of the human brain. Here, 2D transition metal di-chalcogenide (MoS 2 ) neuristors are designed to mimic intracellular ion endocytosis-exocytosis dynamics/neurotransmitter-release in chemical synapses using three approaches: (i) electronic-mode: a defect modulation approach where the traps at the semiconductor-dielectric interface are perturbed; (ii) ionotronic-mode: where electronic responses are modulated via ionic gating; and (iii) photoactive-mode: harnessing persistent photoconductivity or trap-assisted slow recombination mechanisms. Exploiting a novel multigated architecture incorporating electrical and optical biases, this incarnation not only addresses different charge-trapping probabilities to finely modulate the synaptic weights, but also amalgamates neuromodulation schemes to achieve "plasticity of plasticity-metaplasticity" via dynamic control of Hebbian spike-time dependent plasticity and homeostatic regulation. Coexistence of such multiple forms of synaptic plasticity increases the efficacy of memory storage and processing capacity of artificial neuristors, enabling design of highly efficient novel neural architectures. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
NASA Astrophysics Data System (ADS)
Storms, Max
Membrane systems are among the primary emergent technologies in water treatment process units due to their ease of use, small physical footprint, and high physical rejection. Membrane fouling, the phenomena by which membranes become clogged or generally soiled, is an inhibitor to optimal efficiency in membrane systems. Novel, composite, and modified surface materials must be investigated to determine their efficacy in improving fouling behavior. Ceramic membranes derived from iron oxide nanoparticles called ferroxanes were coated with a superhydrophillic, zwitterionic polymer called poly (sulfobetaine methacrylate) (polySBMA) to form a composite ceramic-polymeric membrane. Membrane samples with and without polySBMA coating were subjected to fouling with a bovine serum albumin solution and fouling was observed by measuring permeate flux at 10 mL intervals. Loss of polySBMA was measured using total organic carbon analysis, and membrane samples were characterized using x-ray diffraction, scanning electron microscopy, and optical profilometry. The coated membrane samples decreased initial fouling rate by 27% and secondary fouling rate by 24%. Similarly, they displayed a 30% decrease in irreversible fouling during the initial fouling stage, and a 27% decrease in irreversible fouling in the secondary fouling stage; however, retention of polySBMA sufficient for improved performance was not conclusive. The addition of chemical disinfectants into drinking water treatment processes results in the formation of compounds called disinfection by-products (DBPs). The formation of DBPs occurs when common chemical disinfectants (i.e. chlorine) react with organic material. The harmful effects of DBP exposure require that they be monitored and controlled for public safety. This work investigated the ability of nanostructured hematite derived from ferroxane nanoparticles to remove organic precursors to DBPs in the form of humic acid via adsorption processes. The results show that pH and ionic strength have an effect on adsorption capacity and mechanism. At lower ionic strengths, the adsorption isotherms are closely correlated with the Freundlich adsorption isotherm model, while at higher ionic strength, the isotherms are closely related to the Langmuir adsorption isotherm model. Lower pH systems facilitate better adsorption capacities than higher pH systems, and lower ionic strength systems facilitate better adsorption than higher ionic strength systems.
NASA Astrophysics Data System (ADS)
Winchester, Andrew; Ghosh, Sujoy; Turner, Ben; Zhang, X. F.; Talapatra, Saikat
2012-02-01
In this work we will present the use of Multi Walled Carbon Nanotubes (MWNT) directly grown on inconel substrates via chemical vapor deposition, as electrode materials for electrochemical double layer capacitors (EDLC). The performance of the MWNT EDLC electrodes were investigated using two electrolytes, an organic electrolyte, tetraethylammonium tetrafluoroborate in propylene carbonate (Et4NBF4 in PC), and a room temperature ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM-PF6). Cyclic voltammetry, galvanostatic charge-discharge, and electrochemical impedance spectroscopy measurements to obtain values for the capacitance and internal resistance of these devices will be presented and compared.
Livi, Sébastien; Lins, Luanda Chaves; Peter, Jakub; Kredatusova, Jana; Pruvost, Sébastien
2017-01-01
In this work, phosphonium ionic liquids (ILs) based on tetra-alkylphosphonium cations combined with carboxylate, phosphate and phosphinate anions, were used for organic modification of layered double hydroxide (LDH). Two different amounts (2 and 5 wt %) of the organically modified LDHs were mixed with poly(butylene adipate-co-terephthalate) (PBAT) matrix by melt extrusion. All prepared PBAT/IL-modified-LDH composites exhibited increased mechanical properties (20–50% Young’s modulus increase), decreased water vapor permeability (30–50% permeability coefficient reduction), and slight decreased crystallinity (10–30%) compared to the neat PBAT. PMID:28956811
[Architecture of receptor-operated ionic channels of biological membranes].
Bregestovski, P D
2011-01-01
Ion channels of biological membranes are the key proteins, which provide bioelectric functioning of living systems. These proteins are homo- or heterooligomers assembled from several identical or different subunits. Understanding the architectural organization and functioning of ion channels has been significantly extended due to resolving the crystal structure of several types of voltage-gated and receptor-operated channels. This review summarizes the information obtained from crystal structures of potassium, nicotinic acetylcholine receptor, P2X, and other ligand-gated ion channels. Despite the differences in the function, topology, ionic selectivity, and the subunit stoichiometry, a high similarity in the principles of organization of these macromolecular complexes has been revealed.
Xue, Juan Qin; Liu, Ni Na; Li, Guo Ping; Dang, Long Tao
2017-12-01
This work evaluated the performance of ionic liquids (ILs) in supported liquid membranes in the removal of total cyanide from wastewater. Membranes were characterized by scanning electron microscopy and contact angle measurements to study the membrane morphology and wetting ability. In particular, the effects of operational parameters such as membrane immersion time, feed-phase concentration, and pH on cyanide removal were investigated. ILs are organic salts that are entirely composed of organic cations and either organic or inorganic anions. Since their vapor pressure is negligible, they can be handled easily; this characteristic gives rise to their 'green' nature. In this study, a hydrophobic IL, 1-butyl-3-methylimidazolium hexafluorophosphate ([Bmim]PF 6 ), was immobilized in the pores of a solid polymeric support made of polyvinylidene fluoride. The optimal conditions were as follows: 1 hour membrane immersion time, 312.24 mg/L feed-phase concentration, a feed-phase pH of 4, 3% NaOH solution, and 1 hour stirring time. The cyanide removal was 95.31%. The treatment of cyanide using supported ionic liquid membrane (SILM) technology is a method with potential applications in industry.
Greyling, Guilaume; Pasch, Harald
2017-08-25
Multidetector thermal field-flow fractionation (ThFFF) is shown to be a versatile characterisation platform that can be used to characterise hydrophilic polymers in a variety of organic and aqueous solutions with various ionic strengths. It is demonstrated that ThFFF fractionates isotactic and syndiotactic poly(methacrylic acid) (PMAA) as well as poly(2-vinyl pyridine) (P2VP) and poly(4-vinyl pyridine) (P4VP) according to microstructure in organic solvents and that the ionic strength of the mobile phase has no influence on the retention behaviour of the polymers. With regard to aqueous solutions, it is shown that, despite the weak retention, isotactic and syndiotactic PMAA show different retention behaviours which can qualitatively be attributed to microstructure. Additionally, it is shown that the ionic strength of the mobile phase has a significant influence on the thermal diffusion of polyelectrolytes in aqueous solutions and that the addition of an electrolyte is essential to achieve a microstructure-based separation of P2VP and P4VP in aqueous solutions. Copyright © 2017 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Yang, Peng
The focus of this dissertation is the Molecular Dynamics (MD) simulation study of two different systems. In thefirst system, we study the dynamic process of graphene exfoliation, particularly graphene dispersion using ionic surfactants (Chapter 2). In the second system, we investigate the mesoscopic structure of binary solute/ionic liquid (IL) mixtures through the comparison between simulations and corresponding experiments (Chapter 3 and 4). In the graphene exfoliation study, we consider two separation mechanisms: changing the interlayer distance and sliding away the relative distance of two single-layer graphene sheets. By calculating the energy barrier as a function of separation (interlayer or sliding-away) distance and performing sodium dodecyl sulfate (SDS) structure analysis around graphene surface in SDS surfactant/water + bilayer graphene mixture systems, we find that the sliding-away mechanism is the dominant, feasible separation process. In this process, the SDS-graphene interaction gradually replaces the graphene-graphene Van der Waals (VdW) interaction, and decreases the energy barrier until almost zero at critical SDS concentration. In solute/IL study, we investigate nonpolar (CS2) and dipolar (CH 3CN) solute/IL mixture systems. MD simulation shows that at low concentrations, IL is nanosegregated into an ionic network and nonpolar domain. It is also found that CS2 molecules tend to be localized into the nonpolar domain, while CH3CN interacts with nonpolar domain as well as with the charged head groups in the ionic network because of its amphiphilicity. At high concentrations, CH3CN molecules eventually disrupt the nanostructural organization. This dissertation is organized in four chapters: (1) introduction to graphene, ionic liquids and the methodology of MD; (2) MD simulation of graphene exfoliation; (3) Nanostructural organization in acetonitrile/IL mixtures; (4) Nanostructural organization in carbon disulfide/IL mixtures; (5) Conclusions. Results of MD simulations of liquid mixture systems car-ried out in this research explain observed experiments and show the details of nanostructural organizations in small solute molecules/IL mixture. Additionally, the research successfully reveals the correct mechanism of graphene exfoliation process in liquid solution. (This will be summarized in Chapter 5.) The research presented in this dissertation enhances our understanding of the microscopic behaviors in complex liquid systems as well as the theoretical method to explore them.
Perosa, Alvise; Guidi, Sandro; Cattelan, Lisa
2016-01-01
Summary The use of ionic liquids (ILs) as organocatalysts is reviewed for transesterification reactions, specifically for the conversion of nontoxic compounds such as dialkyl carbonates to both linear mono-transesterification products or alkylene carbonates. An introductory survey compares pros and cons of classic catalysts based on both acidic and basic systems, to ionic liquids. Then, innovative green syntheses of task-specific ILs and their representative applications are introduced to detail the efficiency and highly selective outcome of ILs-catalyzed transesterification reactions. A mechanistic hypothesis is discussed by the concept of cooperative catalysis based on the dual (electrophilic/nucleophilic) activation of reactants. PMID:27829898
NASA Astrophysics Data System (ADS)
Martinez, Mathieu; Molmeret, Yannick; Cointeaux, Laure; Iojoiu, Cristina; Leprêtre, Jean-Claude; El Kissi, Nadia; Judeinstein, Patrick; Sanchez, Jean-Yves
The paper deals with the synthesis and characterisation of proton-conducting ionic liquids (PCILs) and their polymer electrolytes obtained by blending modified Nafion membranes with different concentrations of PCILs. The PCILs are obtained by the neutralization of triethylamine with different organic acids. The first part of the paper studies the influence of acidity and acid structure on PCIL thermal and electrochemical performance, while the second part examines membrane conductivity and reveals it to depend more on PCIL structure than on its intrinsic conductivity. At 130 °C, conductivities exceeding 10 mS cm -1 were obtained in fully anhydrous conditions.
Ionizing Organic Compound Based Nanocomposites for Efficient Gamma-Ray Sensor
NASA Technical Reports Server (NTRS)
Singh, N. B.; Dayal, Vishall; Su, Ching-Hua; Arnold, Bradley; Choa, Fow-Sen; Kabandana, Monia G. K.; House, David
2017-01-01
Thin film and nanocrystalline materials of oxides have been very attractive choice as low cost option for gamma-ray detection and have shown great promise. Our studies on pure oxide films indicated that thickness and microstructure have pronounced effect on sensitivity. Since the interaction of gamma-ray with composites involves all three interaction processes; photoelectric effect, Compton scattering, and pair production, composites containing ionic organics have better chance for enhancing sensitivity. In the composites of ionizing organics oxidation effect of unusual oxides changes much faster and hence increases the sensitivity of radiation. In this study, we have used nickel oxide and titanium oxide in ionic organics to develop composite materials for low energy gamma-ray sensing. We prepared composites containing ethylene carbonate and evaluated the effect of commercial Cs-137 radiation source by studying current-voltage relationship at several frequencies. Radiated samples showed higher resistivity compared to as prepared composites.
Dong, Bing-zhi; Zhang, Jia-li; He, Chang
2016-05-15
The influences of ozone dosage, pH and ionic strength on the formation of Assimilable Organic Carbon (AOC) during ozonation were investigated. The result demonstrated that within the range of 1-5 mg · L⁻¹ O₃, the formation of AOC increased with increasing ozone dosage, but higher ozone dosage (9 mg · L⁻¹) resulted in reduction of AOC formation. AOC formation increased with higher pH but decreased with increasing ionic strength. The result also showed that AOC formation with hydrophobic fraction (HPO) was the most, followed by transphilic fraction (TPI), and charged hydrophilic fraction (CHPI), while neutral hydrophilic fraction (NHPI) was the least. It was found that AOC formation related closely with SUVA of small molecular weight organics, and the lower SUVA produced more AOC.
RM-SORN: a reward-modulated self-organizing recurrent neural network.
Aswolinskiy, Witali; Pipa, Gordon
2015-01-01
Neural plasticity plays an important role in learning and memory. Reward-modulation of plasticity offers an explanation for the ability of the brain to adapt its neural activity to achieve a rewarded goal. Here, we define a neural network model that learns through the interaction of Intrinsic Plasticity (IP) and reward-modulated Spike-Timing-Dependent Plasticity (STDP). IP enables the network to explore possible output sequences and STDP, modulated by reward, reinforces the creation of the rewarded output sequences. The model is tested on tasks for prediction, recall, non-linear computation, pattern recognition, and sequence generation. It achieves performance comparable to networks trained with supervised learning, while using simple, biologically motivated plasticity rules, and rewarding strategies. The results confirm the importance of investigating the interaction of several plasticity rules in the context of reward-modulated learning and whether reward-modulated self-organization can explain the amazing capabilities of the brain.
Wei, Xuan; Sun, Ping; Yang, Shenghong; Zhao, Lei; Wu, Jing; Li, Fengyun; Pu, Qiaosheng
2016-07-29
Plastic microchips can significantly reduce the fabrication cost but the adsorption of some analytes limits their application. In this work, background electrolyte containing ionic polymer and high content of organic solvent was adopted to eliminate the analyte adsorption and achieve highly efficient separation in microchip electrophoresis. Two dyes, rhodamine 6G (Rh6G) and rhodamine B (RhB) were used as the model analytes. By using methanol as the organic solvent and polyacrylic acid (PAA) as a multifunctional additive, successful separation of the two dyes within 75μm id. microchannels was realized. The role of PAA is multiple, including viscosity regulator, selectivity modifier and active additive for counteracting analyte adsorption on the microchannel surface. The number of theoretical plate of 7.0×10(5)/m was attained within an effective separation distance of 2cm using background electrolyte consisting 80% methanol, 0.36% PAA and 30mmol/L phosphate at pH 5.0. Under optimized conditions, relative standard deviations of Rh6G and RhB detection (n=5) were no more than 1.5% for migration time and 2.0% for peak area, respectively. The limit of detection (S/N=3) was 0.1nmol/L for Rh6G. The proposed technique was applied in the determination of both Rh6G and RhB in chilli powder and lipstick samples with satisfactory recoveries of 81.3-103.7%. Copyright © 2016 Elsevier B.V. All rights reserved.
O'Connor, Isabel A; Golsteijn, Laura; Hendriks, A Jan
2016-12-15
Marine plastic debris are found worldwide in oceans and coastal areas. They degrade only slowly and contain chemicals added during manufacture or absorbed from the seawater. Therefore, they can pose a long-lasting contaminant source and potentially transfer chemicals to marine organisms when ingested. In order to assess their risk, the contaminant concentration in the plastics needs to be estimated and differences understood. We collected from literature plastic water partition coefficients of various organic chemicals for seven plastic types: polydimethylsiloxane (PDMS), high-density, low-density and ultra-high molecular weight polyethylene (LDPE, HDPE, UHMWPE), polystyrene (PS), polypropylene (PP), and polyvinyl chloride (PVC). Most data was available for PDMS (1060) and LDPE (220), but much less for the remaining plastics (73). Where possible, regression models were developed and the partitioning was compared between the different plastic types. The partitioning of chemicals follows the order of LDPE≈HDPE≥PP>PVC≈PS. Data describing the impact of weathering are urgently needed. Copyright © 2016 Elsevier Ltd. All rights reserved.
Complex hydrides as room-temperature solid electrolytes for rechargeable batteries
NASA Astrophysics Data System (ADS)
de Jongh, P. E.; Blanchard, D.; Matsuo, M.; Udovic, T. J.; Orimo, S.
2016-03-01
A central goal in current battery research is to increase the safety and energy density of Li-ion batteries. Electrolytes nowadays typically consist of lithium salts dissolved in organic solvents. Solid electrolytes could facilitate safer batteries with higher capacities, as they are compatible with Li-metal anodes, prevent Li dendrite formation, and eliminate risks associated with flammable organic solvents. Less than 10 years ago, LiBH4 was proposed as a solid-state electrolyte. It showed a high ionic conductivity, but only at elevated temperatures. Since then a range of other complex metal hydrides has been reported to show similar characteristics. Strategies have been developed to extend the high ionic conductivity of LiBH4 down to room temperature by partial anion substitution or nanoconfinement. The present paper reviews the recent developments in complex metal hydrides as solid electrolytes, discussing in detail LiBH4, strategies towards for fast room-temperature ionic conductors, alternative compounds, and first explorations of implementation of these electrolytes in all-solid-state batteries.
Ionic Liquid/Metal-Organic Framework Composites: From Synthesis to Applications.
Kinik, Fatma Pelin; Uzun, Alper; Keskin, Seda
2017-07-21
Metal-organic frameworks (MOFs) have been widely studied for different applications owing to their fascinating properties such as large surface areas, high porosities, tunable pore sizes, and acceptable thermal and chemical stabilities. Ionic liquids (ILs) have been recently incorporated into the pores of MOFs as cavity occupants to change the physicochemical properties and gas affinities of MOFs. Several recent studies have shown that IL/MOF composites show superior performances compared with pristine MOFs in various fields, such as gas storage, adsorption and membrane-based gas separation, catalysis, and ionic conductivity. In this review, we address the recent advances in syntheses of IL/MOF composites and provide a comprehensive overview of their applications. Opportunities and challenges of using IL/MOF composites in many applications are reviewed and the requirements for the utilization of these composite materials in real industrial processes are discussed to define the future directions in this field. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Gas-liquid interface of room-temperature ionic liquids.
Santos, Cherry S; Baldelli, Steven
2010-06-01
The organization of ions at the interface of ionic liquids and the vacuum is an ideal system to test new ideas and concepts on the interfacial chemistry of electrolyte systems in the limit of no solvent medium. Whilst electrolyte systems have numerous theoretical and experimental methods used to investigate their properties, the ionic liquids are relatively new and our understanding of the interfacial properties is just beginning to be explored. In this critical review, the gas-liquid interface is reviewed, as this interface does not depend on the preparation of another medium and thus produces a natural interface. The interface has been investigated by sum frequency generation vibrational spectroscopy and ultra-high vacuum techniques. The results provide a detailed molecular-level view of the surface composition and structure. These have been complemented by theoretical studies. The combinations of treatments on this interface are starting to provide a somewhat convergent description of how the ions are organized at this neat interface (108 references).
Flexible single-layer ionic organic-inorganic frameworks towards precise nano-size separation
NASA Astrophysics Data System (ADS)
Yue, Liang; Wang, Shan; Zhou, Ding; Zhang, Hao; Li, Bao; Wu, Lixin
2016-02-01
Consecutive two-dimensional frameworks comprised of molecular or cluster building blocks in large area represent ideal candidates for membranes sieving molecules and nano-objects, but challenges still remain in methodology and practical preparation. Here we exploit a new strategy to build soft single-layer ionic organic-inorganic frameworks via electrostatic interaction without preferential binding direction in water. Upon consideration of steric effect and additional interaction, polyanionic clusters as connection nodes and cationic pseudorotaxanes acting as bridging monomers connect with each other to form a single-layer ionic self-assembled framework with 1.4 nm layer thickness. Such soft supramolecular polymer frameworks possess uniform and adjustable ortho-tetragonal nanoporous structure in pore size of 3.4-4.1 nm and exhibit greatly convenient solution processability. The stable membranes maintaining uniform porous structure demonstrate precisely size-selective separation of semiconductor quantum dots within 0.1 nm of accuracy and may hold promise for practical applications in selective transport, molecular separation and dialysis systems.
Computational modeling of neural plasticity for self-organization of neural networks.
Chrol-Cannon, Joseph; Jin, Yaochu
2014-11-01
Self-organization in biological nervous systems during the lifetime is known to largely occur through a process of plasticity that is dependent upon the spike-timing activity in connected neurons. In the field of computational neuroscience, much effort has been dedicated to building up computational models of neural plasticity to replicate experimental data. Most recently, increasing attention has been paid to understanding the role of neural plasticity in functional and structural neural self-organization, as well as its influence on the learning performance of neural networks for accomplishing machine learning tasks such as classification and regression. Although many ideas and hypothesis have been suggested, the relationship between the structure, dynamics and learning performance of neural networks remains elusive. The purpose of this article is to review the most important computational models for neural plasticity and discuss various ideas about neural plasticity's role. Finally, we suggest a few promising research directions, in particular those along the line that combines findings in computational neuroscience and systems biology, and their synergetic roles in understanding learning, memory and cognition, thereby bridging the gap between computational neuroscience, systems biology and computational intelligence. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.
The American Association of Plastic Surgeons Recent History, with a Review of the Past.
Lawrence, W Thomas
2016-07-01
The American Association of Plastic Surgeons was founded in 1921 and is the oldest of the plastic surgery societies. It was born out of the enthusiasm of reconstructive surgeons who had recently increased in numbers and expanded the scope of their activities as a result of the challenges posed by battle-injured soldiers during World War I. Early meetings were small, focused exclusively on the head and neck, and often included live surgical demonstrations. The Association has grown in size and scope with time, but it has maintained its academic focus. This article focuses on the most recent 15 years of the Association's history, as prior publications have chronicled the history of the organization up to 2000. The organization has remained robust in the new millennium, with the national meetings being its most prominent activity. The format of the meetings has continually been improved to remain relevant and of interest to the membership and other attendees. The organization continues to support the development of young academic plastic surgeons through the Academic Scholars Program. It has established new programs such as the Constable Fellowship to support international exchange and has also sponsored two consensus conferences to help define standards of care in plastic surgery-related issues. The Association annually recognizes significant contributors to the field through the variety of awards that it bestows as well. The mission of the American Association of Plastic Surgeons is to provide scholarly leadership in plastic surgery, and the organization continues to successfully accomplish this mission.
Sieling, Fred; Bédécarrats, Alexis; Simmers, John; Prinz, Astrid A; Nargeot, Romuald
2014-05-05
Rewarding stimuli in associative learning can transform the irregularly and infrequently generated motor patterns underlying motivated behaviors into output for accelerated and stereotyped repetitive action. This transition to compulsive behavioral expression is associated with modified synaptic and membrane properties of central neurons, but establishing the causal relationships between cellular plasticity and motor adaptation has remained a challenge. We found previously that changes in the intrinsic excitability and electrical synapses of identified neurons in Aplysia's central pattern-generating network for feeding are correlated with a switch to compulsive-like motor output expression induced by in vivo operant conditioning. Here, we used specific computer-simulated ionic currents in vitro to selectively replicate or suppress the membrane and synaptic plasticity resulting from this learning. In naive in vitro preparations, such experimental manipulation of neuronal membrane properties alone increased the frequency but not the regularity of feeding motor output found in preparations from operantly trained animals. On the other hand, changes in synaptic strength alone switched the regularity but not the frequency of feeding output from naive to trained states. However, simultaneously imposed changes in both membrane and synaptic properties reproduced both major aspects of the motor plasticity. Conversely, in preparations from trained animals, experimental suppression of the membrane and synaptic plasticity abolished the increase in frequency and regularity of the learned motor output expression. These data establish direct causality for the contributions of distinct synaptic and nonsynaptic adaptive processes to complementary facets of a compulsive behavior resulting from operant reward learning. Copyright © 2014 Elsevier Ltd. All rights reserved.
Mu'min, Gea Fardias; Prawisudha, Pandji; Zaini, Ilman Nuran; Aziz, Muhammad; Pasek, Ari Darmawan
2017-09-01
This study employs wet torrefaction process (also known as hydrothermal) at low temperature. This process simultaneously acts as waste processing and separation of mixed waste, for subsequent utilization as an alternative fuel. The process is also applied for the delamination and separation of non-recyclable laminated aluminum waste into separable aluminum and plastic. A 2.5-L reactor was used to examine the wet torrefaction process at temperatures below 200°C. It was observed that the processed mixed waste was converted into two different products: a mushy organic part and a bulky plastic part. Using mechanical separation, the two products can be separated into a granular organic product and a plastic bulk for further treatment. TGA analysis showed that no changes in the plastic composition and no intrusion from plastic fraction to the organic fraction. It can be proclaimed that both fractions have been completely separated by wet torrefaction. The separated plastic fraction product obtained from the wet torrefaction treatment also contained relatively high calorific value (approximately 44MJ/kg), therefore, justifying its use as an alternative fuel. The non-recyclable plastic fraction of laminated aluminum was observed to be delaminated and separated from its aluminum counterpart at a temperature of 170°C using an additional acetic acid concentration of 3%, leaving less than 25% of the plastic content in the aluminum part. Plastic products from both samples had high calorific values of more than 30MJ/kg, which is sufficient to be converted and used as a fuel. Copyright © 2017 Elsevier Ltd. All rights reserved.
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.
Mesoscale studies of ionic closed membranes with polyhedral geometries
2016-07-25
assembled ionic amphiphiles.4 The most commonly observed polyhedral symmetry in self-organized homogeneous structures is the icosahedron, which has the...Possible buckled structures can be obtained considering components A, B with intermediate compositions f of the B component such that the stable shape...lines aids the faceting of the shell into a polyhedral structure often with three-fold vertices. Such vertices are joined together by sharp edges
ERIC Educational Resources Information Center
Hu, Jun; Yin, Jinxiang; Lin, Tianshu; Li, Guangtao
2012-01-01
A new solvent-free microwave experiment to synthesize the ionic liquid 1-hexadecyl-3-methylimidazolium bromide (HDMIm-Br) in high yield is presented. The structure is confirmed by IR and [superscript 1]H NMR spectra. HDMIm-Br is then used to prepare an organic-inorganic mesoporous material MCM-41. The microscopic arrangements of mesoporous…
Xu, Ling; Yan, Shihai; Choi, Eun-Young; Lee, Jin Yong; Kwon, Young-Uk
2009-06-21
Ni(OAc)(2)-H(3)BTC system in various ionic liquids, [RMI]X (R = ethyl, n-propyl, n-butyl; X = Cl, Br, I), produced five MOFs in two structure types; their relative thermodynamic stability varies with the size of RMI(+), and the X(-) ions govern the kinetic factors so that their combination effects determine the final product.
Reguyal, Febelyn; Sarmah, Ajit K
2018-07-01
Recent studies have shown the widespread occurrence of pharmaceuticals in the aquatic environment leading to increasing global concern on their potential adverse effects in the environment and public health. In this study, we evaluated the use of magnetic biochar derived from pine sawdust, one of New Zealand's major wood wastes, to remove an emerging contaminant, sulfamethoxazole (SMX), at different pH, ionic strength, natural organic matter (NOM) and a competing compound, 17α-ethinylestradiol (EE2). In single-solute system, the sorption of SMX onto magnetic biochar was found to be highly pH-dependent and slightly increased with increase in ionic strength. However, the effects of pH, ionic strength and NOM were relatively insignificant compared to the sorption inhibition caused by EE2 in binary-solute system. Both SMX and EE2 sorption onto the highly carbonised biochar in magnetic biochar were postulated to be due to the π-π electron donor acceptor and hydrophobic interaction. EE2 is more hydrophobic than SMX. Hence, strong competition between these compounds was identified where EE2 markedly inhibited the sorption of SMX onto magnetic biochar in all artificial environmental conditions studied. Copyright © 2018 Elsevier B.V. All rights reserved.
This document contains a methodology for developing interstitial water remediation goals (IWRGs) for nonionic organic pollutants (toxicants) in sediments for the protection of benthic organisms. The document provides the basis for using the final chronic values (FCVs) from EPA’s...
Excimer Formation Dynamics of Dipyrenyldecane in Structurally Different Ionic Liquids.
Yadav, Anita; Pandey, Siddharth
2017-12-07
Ionic liquids, being composed of ions alone, may offer alternative pathways for molecular aggregation. These pathways could be controlled by the chemical structure of the cation and the anion of the ionic liquids. Intramolecular excimer formation dynamics of a bifluorophoric probe, 1,3-bis(1-pyrenyl)decane [1Py(10)1Py], where the fluorophoric pyrene moieties are separated by a long decyl chain, is investigated in seven different ionic liquids in 10-90 °C temperature range. The long alkyl separator allows for ample interaction with the solubilizing milieu prior to the formation of the excimer. The ionic liquids are composed of two sets, one having four ionic liquids of 1-butyl-3-methylimidazolium cation ([bmim + ]) with different anions and the other having four ionic liquids of bis(trifluoromethylsulfonyl)imide anion ([Tf 2 N - ]) with different cations. The excimer-to-monomer emission intensity ratio (I E /I M ) is found to increase with increasing temperature in sigmoidal fashion. Chemical structure of the ionic liquid controls the excimer formation efficiency, as I E /I M values within ionic liquids with the same viscosities are found to be significantly different. The excited-state intensity decay kinetics of 1Py(10)1Py in ionic liquids do not adhere to a simplistic Birk's scheme, where only one excimer conformer forms after excitation. The apparent rate constants of excimer formation (k a ) in highly viscous ionic liquids are an order of magnitude lower than those reported in organic solvents. In general, the higher the viscosity of the ionic liquid, the more sensitive is the k a to the temperature with higher activation energy, E a . The trend in E a is found to be similar to that for activation energy of the viscous flow (E a,η ). Stokes-Einstein relationship is not followed in [bmim + ] ionic liquids; however, with the exception of [choline][Tf 2 N], it is found to be followed in [Tf 2 N - ] ionic liquids suggesting the cyclization dynamics of 1Py(10)1Py to be diffusion-controlled and to depend on the viscosity of the ionic liquid irrespective of the identity of the cation. The dependence of ionic liquid structure on cyclization dynamics to form intramolecular excimer is amply highlighted.
Wang, Lei; Gong, Xinying; Wang, Ruonan; Gan, Zhiwei; Lu, Yuan; Sun, Hongwen
2017-09-15
Ionic liquids have been used to efficiently extract a wide range of polar and nonpolar organic contaminants from water. In this study, imidazole ionic liquids immobilized on silica gel were synthesized through a chemical bonding method, and the immobilized dodecylimidazolium ionic liquid was selected as the receiving phase material in a POCIS (polar organic chemical integrative sampler) like passive sampler to monitor five perfluoroalkyl substances (PFASs) in water. Twenty-one days of integrative accumulation was conducted in laboratory scale experiments, and the accumulated PFASs in the samplers were eluted and analyzed by high performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS). The partitioning coefficients of most PFASs between sampler sorbents and water in the immobilized ionic liquid (IIL)-sampler were higher than those in the HLB-sampler, especially for compounds with shorter alkyl chains. The effects of flow velocity, temperature, dissolved organic matter (DOM) and pH on the uptake of these analytes were also evaluated. Under the experimental conditions, the uptake of PFASs in the IIL-sampler slightly increased with the flow velocity and temperature, while different influences of DOM and pH on the uptake of PFAS homologues with short or long chains were observed. The designed IIL-samplers were applied in the influent and effluent of a wastewater treatment plant. All five PFASs could be accumulated in the samplers, with concentrations ranging from 6.5×10 -3 -3.6×10 -1 nmol/L in the influent and from 1.3×10 -2 -2.2×10 -1 nmol/L in the effluent. The calculated time-weighted average concentrations of most PFASs fit well with the detected concentrations of the active sampling, indicating the applicability of the IIL-sampler in monitoring these compounds in water. Copyright © 2017 Elsevier B.V. All rights reserved.
Park, Jong Baek; Isik, Mehmet; Park, Hea Jung; Jung, In Hwan; Mecerreyes, David; Hwang, Do-Hoon
2018-02-07
Interfacial layers play a critical role in building up the Ohmic contact between electrodes and functional layers in organic photovoltaic (OPV) solar cells. These layers are based on either inorganic oxides (ZnO and TiO 2 ) or water-soluble organic polymers such as poly[(9,9-dioctyl-2,7-fluorene)-alt-(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)] and polyethylenimine ethoxylated (PEIE). In this work, we have developed a series of novel poly(ionic liquid) nonconjugated block copolymers for improving the performance of inverted OPV cells by using them as work function modifiers of the indium tin oxide (ITO) cathode. Four nonconjugated polyelectrolytes (n-CPEs) based on polystyrene and imidazolium poly(ionic liquid) (PSImCl) were synthesized by reversible addition-fragmentation chain transfer polymerization. The ratio of hydrophobic/hydrophilic block copolymers was varied depending on the ratio of polystyrene to the PSImCl block. The ionic density, which controls the work function of the electrode by forming an interfacial dipole between the electrode and the block copolymers, was easily tuned by simply changing the PSImCl molar ratio. The inverted OPV device with the ITO/PS 29 -b-PSImCl 60 cathode achieved the best power conversion efficiency (PCE) of 7.55% among the synthesized block copolymers, exhibiting an even higher PCE than that of the reference OPV device with PEIE (7.30%). Furthermore, the surface properties of the block copolymers films were investigated by contact angle measurements to explore the influence of the controlled hydrophobic/hydrophilic characters on the device performances.
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.
Plastic fiber optics for micro-imaging of fluorescence signals in living cells
NASA Astrophysics Data System (ADS)
Sakurai, Takashi; Natsume, Mitsuo; Koida, Kowa
2015-03-01
The fiber-coupled microscope (FCM) enables in vivo imaging at deep sites in the tissues or organs that other optical techniques are unable to reach. To develop FCM-based intravital imaging, we employed a plastic optical fiber (POF) bundle that included more than 10,000-units of polystyrene core and polymethyl methacrylate cladding. Each POF had a diameter of less than 5 μm the tip of the bundle was less than 0.5 mm wide, and the flexible wire had a length of 1,000 mm. The optical performance of the plastic FCM was sufficient for detection of significant signal changes in an acinus of rat pancreas labeled with a calcium ion-sensitive fluorescent dye. In the future, the potential power of plastic FCM is expected to increase, enabling analysis of structure and organization of specific functions in live cells within vulnerable organs.
Organic micropollutants in marine plastics debris from the open ocean and remote and urban beaches.
Hirai, Hisashi; Takada, Hideshige; Ogata, Yuko; Yamashita, Rei; Mizukawa, Kaoruko; Saha, Mahua; Kwan, Charita; Moore, Charles; Gray, Holly; Laursen, Duane; Zettler, Erik R; Farrington, John W; Reddy, Christopher M; Peacock, Emily E; Ward, Marc W
2011-08-01
To understand the spatial variation in concentrations and compositions of organic micropollutants in marine plastic debris and their sources, we analyzed plastic fragments (∼10 mm) from the open ocean and from remote and urban beaches. Polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), dichloro-diphenyl-trichloroethane and its metabolites (DDTs), polybrominated diphenyl ethers (PBDEs), alkylphenols and bisphenol A were detected in the fragments at concentrations from 1 to 10,000 ng/g. Concentrations showed large piece-to-piece variability. Hydrophobic organic compounds such as PCBs and PAHs were sorbed from seawater to the plastic fragments. PCBs are most probably derived from legacy pollution. PAHs showed a petrogenic signature, suggesting the sorption of PAHs from oil slicks. Nonylphenol, bisphenol A, and PBDEs came mainly from additives and were detected at high concentrations in some fragments both from remote and urban beaches and the open ocean. Copyright © 2011 Elsevier Ltd. All rights reserved.
Szymański, Krzysztof; Petrache, Horia I
2011-04-14
Re-examination of dynamical ionic polarizabilities in water solutions leads to the formulation of a solution function r(c), which combines the indices of refraction and mass densities of solutions. We show that this function should be independent of ionic concentration if the composite polarizabilities of hydrated solute clusters are constant. Using existing experimental data for a number of aqueous salt and organic solutions, we find that the r(c) function is either constant or varies linearly with concentration, in most cases with negligible slope. We use this function to compare ionic polarizabilities of crystals and aqueous solutions and to highlight how solute polarizabilities at infinite dilution scale with the electronic valence shell of cations and anions. The proposed r(c) function can be used generally to verify the consistency of experimental measurements and of simulation results, and it provides a test of assumptions in current theories of ionic polarizabilities.
Flexible thin-film battery based on solid-like ionic liquid-polymer electrolyte
NASA Astrophysics Data System (ADS)
Li, Qin; Ardebili, Haleh
2016-01-01
The development of high-performance flexible batteries is imperative for several contemporary applications including flexible electronics, wearable sensors and implantable medical devices. However, traditional organic liquid-based electrolytes are not ideal for flexible batteries due to their inherent safety and stability issues. In this study, a non-volatile, non-flammable and safe ionic liquid (IL)-based polymer electrolyte film with solid-like feature is fabricated and incorporated in a flexible lithium ion battery. The ionic liquid is 1-Ethyl-3-methylimidazolium dicyanamide (EMIMDCA) and the polymer is composed of poly(vinylidene fluoride-co-hexafluoropropene) (PVDF-HFP). The electrolyte exhibits good thermal stability (i.e. no weight loss up to 300 °C) and relatively high ionic conductivity (6 × 10-4 S cm-1). The flexible thin-film lithium ion battery based on solid-like electrolyte film is encapsulated using a thermal-lamination process and demonstrates excellent electrochemical performance, in both flat and bent configurations.
Complex Ion Dynamics in Carbonate Lithium-Ion Battery Electrolytes
DOE Office of Scientific and Technical Information (OSTI.GOV)
Ong, Mitchell T.; Bhatia, Harsh; Gyulassy, Attila G.
Li-ion battery performance is strongly influenced by ionic conductivity, which depends on the mobility of the Li ions in solution, and is related to their solvation structure. In this work, we have performed first-principles molecular dynamics (FPMD) simulations of a LiPF6 salt solvated in different Li-ion battery organic electrolytes. We employ an analytical method using relative angles from successive time intervals to characterize complex ionic motion in multiple dimensions from our FPMD simulations. We find different characteristics of ionic motion on different time scales. We find that the Li ion exhibits a strong caging effect due to its strong solvationmore » structure, while the counterion, PF6– undergoes more Brownian-like motion. Lastly, our results show that ionic motion can be far from purely diffusive and provide a quantitative characterization of the microscopic motion of ions over different time scales.« less
Complex Ion Dynamics in Carbonate Lithium-Ion Battery Electrolytes
Ong, Mitchell T.; Bhatia, Harsh; Gyulassy, Attila G.; ...
2017-03-06
Li-ion battery performance is strongly influenced by ionic conductivity, which depends on the mobility of the Li ions in solution, and is related to their solvation structure. In this work, we have performed first-principles molecular dynamics (FPMD) simulations of a LiPF6 salt solvated in different Li-ion battery organic electrolytes. We employ an analytical method using relative angles from successive time intervals to characterize complex ionic motion in multiple dimensions from our FPMD simulations. We find different characteristics of ionic motion on different time scales. We find that the Li ion exhibits a strong caging effect due to its strong solvationmore » structure, while the counterion, PF6– undergoes more Brownian-like motion. Lastly, our results show that ionic motion can be far from purely diffusive and provide a quantitative characterization of the microscopic motion of ions over different time scales.« less
Zhang, Rui; Wang, Chuanliu; Yue, Qiaohong; Zhou, Tiecheng; Li, Na; Zhang, Hanqi; Hao, Xiaoke
2014-11-01
An ionic liquid foam floatation coupled with ionic liquid dispersive liquid-liquid microextraction method was proposed for the extraction and concentration of 17-α-estradiol, 17-β-estradiol-benzoate, and quinestrol in environmental water samples by high-performance liquid chromatography with fluorescence detection. 1-Hexyl-3-methylimidazolium tetrafluoroborate was applied as foaming agent in the foam flotation process and dispersive solvent in microextraction. The introduction of the ion-pairing and salting-out agent NH4 PF6 was beneficial to the improvement of recoveries for the hydrophobic ionic liquid phase and analytes. Parameters of the proposed method including concentration of 1-hexyl-3-methylimidazolium tetrafluoroborate, flow rate of carrier gas, floatation time, types and concentration of ionic liquids, salt concentration in samples, extraction time, and centrifugation time were evaluated. The recoveries were between 98 and 105% with relative standard deviations lower than 7% for lake water and well water samples. The isolation of the target compounds from the water was found to be efficient, and the enrichment factors ranged from 4445 to 4632. This developing method is free of volatile organic solvents compared with regular extraction. Based on the unique properties of ionic liquids, the application of foam floatation, and dispersive liquid-liquid microextraction was widened. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Phenotypic plasticity and longevity in plants and animals: cause and effect?
Borges, Renee M
2009-10-01
Immobile plants and immobile modular animals outlive unitary animals. This paper discusses competing but not necessarily mutually exclusive theories to explain this extreme longevity, especially from the perspective of phenotypic plasticity. Stem cell immortality, vascular autonomy, and epicormic branching are some important features of the phenotypic plasticity of plants that contribute to their longevity. Monocarpy versus polycarpy can also influence the kind of senescent processes experienced by plants. How density-dependent phenomena affecting the establishment of juveniles in these immobile organisms can influence the evolution of senescence, and consequently longevity, is reviewed and discussed. Whether climate change scenarios will favour long-lived or short-lived organisms, with their attendant levels of plasticity, is also presented.
Wan, Chang Jin; Zhu, Li Qiang; Zhou, Ju Mei; Shi, Yi; Wan, Qing
2014-05-07
Ionic/electronic hybrid devices with synaptic functions are considered to be the essential building blocks for neuromorphic systems and brain-inspired computing. Here, artificial synapses based on indium-zinc-oxide (IZO) transistors gated by nanogranular SiO2 proton-conducting electrolyte films are fabricated on glass substrates. Spike-timing dependent plasticity and paired-pulse facilitation are successfully mimicked in an individual bottom-gate transistor. Most importantly, dynamic logic and dendritic integration established by spatiotemporally correlated spikes are also mimicked in dendritic transistors with two in-plane gates as the presynaptic input terminals.
Furfural production in biphasic media using an acidic ionic liquid as a catalyst.
Peleteiro, Susana; Santos, Valentín; Parajó, Juan C
2016-11-20
Ionic liquids are valuable tools for biorefineries. This study provides an experimental assessment on the utilization of an acidic ionic liquid (1-butyl-3-methylimidazolium hydrogen sulfate) as a catalyst for furfural production in water/solvent media. The substrates employed in experiments were commercial xylose (employed as a reference compound) or hemicellulosic saccharides obtained by hydrothermal processing of Eucalyptus globulus wood (which were employed as produced, after membrane concentration or after freeze-drying). A variety of reaction conditions (defined by temperature, reaction time and type of organic solvent) were considered. The possibility of recycling the catalyst was assessed in selected experiments. Copyright © 2016 Elsevier Ltd. All rights reserved.
Optimizing Ionic Electrolytes for Dye-Sensitized Solar Cells
NASA Astrophysics Data System (ADS)
Fan, Xiaojuan; Hall, Sarah
2009-03-01
Dye-sensitized solar cells DSSCs provide next generation, low cost, and easy fabrication photovoltaic devices based on organic sensitizing molecules, polymer gel electrolyte, and metal oxide semiconductors. One of the key components is the solvent-free ionic liquid electrolyte that has low volatility and high stability. We report a rapid and low cost method to fabricate ionic polymer electrolyte used in DSSCs. Poly(ethylene oxide) (PEO) is blended with imidazolinium salt without any chemical solvent to form a gel electrolyte. Uniform and crack-free porous TiO2 thin films are sensitized by porphrine dye covered by the synthesized gel electrolyte. The fabricated DSSCs are more stable and potentially increase the photo-electricity conversion efficiency.
NASA Astrophysics Data System (ADS)
Benedetto, Antonio; Ballone, Pietro
2018-05-01
Increasing attention is being devoted to the interaction of a new class of organic ionic liquids known as room-temperature ionic liquids (RTILs) with biomolecules, partly because of health and environment concerns, and, even more, for the prospect of exciting new applications in biomedicine, sensing and energy technologies. Here we focus on the interaction between RTILs and phospholipid bilayers that are well-accepted models for bio-membranes. We discuss how neutron scattering has been used to probe both the structure and the dynamics of these systems, and how its integration with molecular dynamics simulation has allowed the determination of the microscopic details of their interaction.
Molecular mobility, morphology, and ion conduction in ionomers for electroactive devices
NASA Astrophysics Data System (ADS)
Tudryn, Gregory J.
A sequential study of ion-containing polymers capable of ion solvation with varied ion content, dielectric constant, and counterions is presented in this dissertation in order to compare ion transport properties in ionomers with various ionic interactions. Structure-property relationships in these ion containing polymers are defined using x-ray scattering, rheology and dielectric spectroscopy, enabling the quantification of ion transport dynamics. Poly(ethylene oxide), (PEO) based ionomers are investigated in order to probe the relation between ion conduction and segmental relaxation, and copolymers of PEO and Poly(tetramethylene oxide), (PTMO) further develop an understanding of the trade-off between ion solvation and segmental dynamics. Ionomers with ionic liquid counterions probe diffuse charge interactions and steric effects on ion transport, and incorporation of ionic liquids into ionomer membranes such as Nafion provides desirable thermal and ion conducting properties which extend the use of such membranes for electroactive devices. PEO ionomers exhibit a strong relation between ionic conductivity and segmental dynamics, providing insight that the glass transition temperature, Tg, dominates the ion conduction mechanism. Increasing temperature induces aggregation of ionic groups as evidenced by the static dielectric constant and X-ray scattering as a function of temperature, revealing the contribution of ionic dipoles in the measured dielectric constant. The trade-off between ion solvation and fast polymer segmental dynamics are quantified in copolymer ionomers of PEO and lower Tg PTMO. While conducting ion content remains nearly unchanged, conductivity is lowered upon incorporation of PTMO, because the vast majority of the PTMO microphase separates from the PEO-rich microdomain that remains continuous and contributes most of the ion conduction. Dielectric constants and X-ray scattering show consistent changes with temperature that suggest a cascading aggregation process in Na ionomers as ionic dipoles thermally randomize and lower the measured dielectric constant of the medium, leading to further aggregation. We observe amplified microphase-separation through ionic groups preferentially solvated by PEO chains, as seen in block copolymers with added salt. Even at 25%PEO / 75%PTMO the ionomers have VFT temperature dependence of conducting ion mobility, meaning that the 25% PEO/ion microphase is still continuous A model is developed to describe the frequency dependent storage and loss modulus and the delay in Rouse motion due to ion association lifetime, as functions of ion content and molecular weight for our low molecular weight ionomers. The ion rearrangement relaxation in dielectric spectroscopy is clearly the ion association lifetime that controls terminal dynamics in linear viscoelasticity, allowing a simple sticky Rouse model, using the most-probable distribution based on NMR Mn, to fully describe master curves of the frequency dependent storage and loss modulus. Using insight from ionic interaction strength, ionic liquids are used as counterions, effectively plasticizing the ionomers without added solvent. Ionic interactions were weakened with increasing counterion size, and with modification of cations using ether-oxygen, promoting self-solvation, which increases conducting ion density by an order of magnitude. Room temperature ionic liquids were subsequently used in combination with NafionRTM membranes as electroactive substrates to correlate ion transport to morphology as a function of volume fraction of ionic liquid. This study illuminated the critical volume uptake of ionic liquid in Nafion, identifying percolation of ionic pathways and a significant increase in dielectric constant at low frequencies, indicating an increase in the number density of ions capable of polarizing at the electrode surface. Consequently, the fundamental information obtained about the structure-property relations of ionomers can be used to predict and design advanced ion-containing polymers to be used in battery membranes and a variety of electroactive devices, including actuators and electromechanical sensors.
Bullock, John D; Warwar, Ronald E; Elder, B Laurel; Khamis, Harry J
2016-05-01
The purposes of this study were to determine whether the contact lens solution RevitaLens Ocutec (containing the antimicrobial agents alexidine and polyquaternium-1) would inhibit Fusarium organisms when heated in ReNu plastic bottles; whether alexidine would inhibit Fusarium organisms when heated in non-ReNu plastic bottles; and whether an alexidine-neutralizing compound leaches from heated ReNu bottles. RevitaLens and an alexidine solution (0.00045%), previously stored in ReNu bottles at room temperature (RT) and 56°C, were incubated with 7 different Fusarium organisms. The alexidine solution was similarly stored in seven non-ReNu plastic bottles and incubated with these same organisms. To determine if an alexidine-neutralizing compound might be leaching from heated ReNu bottles, phosphate-buffered saline (PBS) was incubated at RT and 56°C in ReNu bottles, combined with alexidine, and then tested for anti-Fusarium capability. After being heated in ReNu bottles, RevitaLens retained its anti-Fusarium capability, whereas the alexidine solution did not. The alexidine solution heated in seven non-ReNu plastic bottles retained its anti-Fusarium capability. The alexidine solution retained its anti-Fusarium capability when incubated with a PBS solution that had been heated in ReNu bottles, indicating, microbiologically, that an alexidine-neutralizing compound did not leach from the heated ReNu bottle. Alexidine uniquely fails to inhibit Fusarium organisms when heated in a plastic ReNu bottle, but not in seven other plastic bottles, whereas the anti-Fusarium capability of RevitaLens (containing the antimicrobial agents alexidine and polyquaternium-1) is unaffected by heating in a ReNu bottle. There does not seem to be an alexidine-neutralizing compound leaching from heated ReNu bottles. An interaction between alexidine and its heated ReNu bottle may have been a critical factor in the worldwide ReNu with MoistureLoc-related Fusarium keratitis event of 2004 to 2006.
Development of ionic gels using thiol-based monomers in ionic liquid
NASA Astrophysics Data System (ADS)
Ahmed, Kumkum; Naga, Naofumi; Kawakami, Masaru; Furukawa, Hidemitsu
2016-04-01
Ionic gels (IGs) using ionic liquids (ILs) can propose diverse applications in the field of optics, sensors and separation have opened wide prospects in materials science. ILs have attracted remarkable interest for gel polymer electrolytes and batteries based on their useful properties such as non-volatility, non-flammability, a wide electrochemical window, high thermal stability and a high ionic conductivity. The formation of gel in IL media makes it possible to immobilize ILs within organic or inorganic matrices and to take advantage of their unique properties in the solid state, thus eliminating some shortcomings related to shaping and risk of leakage. In this work for the first time we used multifunctional thiol monomers having uniform structure and good compatibility with the IL of our interest. Therefore we focused on developing thiol monomer-based IGs using multifunctional thiol monomers and acrylate crosslinkers utilizing thiol-ene reaction between monomer and crosslinking molecules in an IL medium and characterize their physico-chemical properties like thermal, conductive, mechanical properties etc.. This work has been focused mainly to improve the mechanical strength of IGs and make prospects of IGs in tribology and lubricants.
Biodegradation of imidazolium ionic liquids by activated sludge microorganisms.
Liwarska-Bizukojc, Ewa; Maton, Cedric; Stevens, Christian V
2015-11-01
Biological properties of ionic liquids (ILs) have been usually tested with the help of standard biodegradation or ecotoxicity tests. So far, several articles on the identification of intermediate metabolites of microbiological decay of ILs have been published. Simultaneously, the number of novel ILs with unrecognized characteristics regarding biodegradability and effect on organisms and environment is still increasing. In this work, seven imidazolium ionic liquids of different chemical structure were studied. Three of them are 1-alkyl-3-methyl-imidazolium bromides, while the other four are tetra- or completely substituted imidazolium iodides. This study focused on the identification of intermediate metabolites of the aforementioned ionic liquids subjected to biodegradation in a laboratory activated sludge system. Both fully substituted ionic liquids and 1-ethyl-3-methyl-imidazolium bromide were barely biodegradable. In the case of two of them, no biotransformation products were detected. The elongation of the alkyl side chain made the IL more susceptible for microbiological decomposition. 1-Decyl-3-methyl-imidazolium bromide was biotransformed most easily. Its primary biodegradation up to 100 % could be achieved. Nevertheless, the cleavage of the imidazolium ring has not been observed.
Simulating chemical reactions in ionic liquids using QM/MM methodology.
Acevedo, Orlando
2014-12-18
The use of ionic liquids as a reaction medium for chemical reactions has dramatically increased in recent years due in large part to the numerous reported advances in catalysis and organic synthesis. In some extreme cases, ionic liquids have been shown to induce mechanistic changes relative to conventional solvents. Despite the large interest in the solvents, a clear understanding of the molecular factors behind their chemical impact is largely unknown. This feature article reviews our efforts developing and applying mixed quantum and molecular mechanical (QM/MM) methodology to elucidate the microscopic details of how these solvents operate to enhance rates and alter mechanisms for industrially and academically important reactions, e.g., Diels-Alder, Kemp eliminations, nucleophilic aromatic substitutions, and β-eliminations. Explicit solvent representation provided the medium dependence of the activation barriers and atomic-level characterization of the solute-solvent interactions responsible for the experimentally observed "ionic liquid effects". Technical advances are also discussed, including a linear-scaling pairwise electrostatic interaction alternative to Ewald sums, an efficient polynomial fitting method for modeling proton transfers, and the development of a custom ionic liquid OPLS-AA force field.
Flegr, Jaroslav
2010-01-13
Darwin's evolutionary theory could easily explain the evolution of adaptive traits (organs and behavioral patterns) in asexual but not in sexual organisms. Two models, the selfish gene theory and frozen plasticity theory were suggested to explain evolution of adaptive traits in sexual organisms in past 30 years. The frozen plasticity theory suggests that sexual species can evolve new adaptations only when their members are genetically uniform, i.e. only after a portion of the population of the original species had split off, balanced on the edge of extinction for several generations, and then undergone rapid expansion. After a short period of time, estimated on the basis of paleontological data to correspond to 1-2% of the duration of the species, polymorphism accumulates in the gene pool due to frequency-dependent selection; and thus, in each generation, new mutations occur in the presence of different alleles and therefore change their selection coefficients from generation to generation. The species ceases to behave in an evolutionarily plastic manner and becomes evolutionarily elastic on a microevolutionary time-scale and evolutionarily frozen on a macroevolutionary time-scale. It then exists in this state until such changes accumulate in the environment that the species becomes extinct. Frozen plasticity theory, which includes the Darwinian model of evolution as a special case--the evolution of species in a plastic state, not only offers plenty of new predictions to be tested, but also provides explanations for a much broader spectrum of known biological phenomena than classic evolutionary theories. This article was reviewed by Rob Knight, Fyodor Kondrashov and Massimo Di Giulio (nominated by David H. Ardell).
Cha, An-Na; Lee, Sang-A; Bae, Sukang; Lee, Sang Hyun; Lee, Dong Su; Wang, Gunuk; Kim, Tae-Wook
2017-01-25
An all-organic composite system was introduced as an active component for organic resistive memory applications. The active layer was prepared by mixing a highly polar plastic-crystalline organic molecule (succinonitrile, SN) into an insulating polymer (poly(methyl methacrylate), PMMA). As increasing concentrations of SN from 0 to 3.0 wt % were added to solutions of different concentrations of PMMA, we observed distinguishable microscopic surface structures on blended films of SN and PMMA at certain concentrations after the spin-casting process. The structures were organic dormant volcanos composed of micron-scale PMMA craters and disk type SN lava. Atomic force microscopy (AFM), cross-sectional transmission electron microscopy (TEM), scanning electron microscopy (SEM), and energy dispersive X-ray spectrometer (EDX) analysis showed that these structures were located in the middle of the film. Self-assembly of the plastic-crystalline molecules resulted in the phase separation of the SN:PMMA mixture during solvent evaporation. The organic craters remained at the surface after the spin-casting process, indicative of the formation of an all-organic composite film. Because one organic crater contains one SN disk, our system has a coplanar monolayer disk composite system, indicative of the simplest composite type of organic memory system. Current-voltage (I-V) characteristics of the composite films with organic craters revealed that our all-organic composite system showed unipolar type resistive switching behavior. From logarithmic I-V characteristics, we found that the current flow was governed by space charge limited current (SCLC). From these results, we believe that a plastic-crystalline molecule-polymer composite system is one of the most reliable ways to develop organic composite systems as potential candidates for the active components of organic resistive memory applications.
ERIC Educational Resources Information Center
Caspar, A.; And Others
1986-01-01
Proposes a two-stage experimental approach that combines preparative chemistry and polymer characterization. Describes the simple organic synthesis of a plasticizer, the dioctylphthalate, and its direct use in the preparation of a styrene/divinylbenzene network copolymer. Discusses how to evaluate the physical properties of the resulting plastic.…
Enhanced performance of dicationic ionic liquid electrolytes by organic solvents.
Li, Song; Zhang, Pengfei; Fulvio Pasquale, F; Hillesheim Patrick, C; Feng, Guang; Dai, Sheng; Cummings Peter, T
2014-07-16
The use of dicationic ionic liquid (DIL) electrolytes in supercapacitors is impeded by the slow dynamics of DILs, whereas the addition of organic solvents into DIL electrolytes improves ion transport and then enhances the power density of supercapacitors. In this work, the influences of organic solvents on the conductivity of DILs and the electrical double layer (EDL) of DIL-based supercapacitors are investigated using classical molecular dynamics simulation. Two types of organic solvents, acetonitrile (ACN) and propylene carbonate (PC), were used to explore the effects of different organic solvents on the EDL structure and capacitance of DIL/organic solvent-based supercapacitors. Firstly, it was found that the conductivity of DIL electrolytes was greatly enhanced in the presence of the organic solvent ACN. Secondly, a stronger adsorption of PC on graphite results in different EDL structures formed by DIL/ACN and DIL/PC electrolytes. The expulsion of co-ions from EDLs was observed in DIL/organic solvent electrolytes rather than neat DILs and this feature is more evident in DIL/PC. Furthermore, the bell-shaped differential capacitance-electric potential curve was not essentially changed by the presence of organic solvents. Comparing DIL/organic solvent electrolytes with neat DILs, the capacitance is slightly increased by organic solvents, which is in agreement with experimental observation.
Plastics Distribution and Degradation on Lake Huron Beaches
NASA Astrophysics Data System (ADS)
Zbyszewski, M.; Corcoran, P.
2009-05-01
The resistivity of plastic debris to chemical and mechanical weathering processes poses a serious threat to the environment. Numerous marine beaches are littered with plastic fragments that entangle and become ingested by organisms including birds, turtles and plankton. Although many studies have been conducted to determine the amount and effects of plastics pollution on marine organisms, relatively little is known about the distribution and quantity of polymer types along lacustrine beaches. Plastic particles sampled from selected beaches on Lake Huron were analyzed using Fourier Transform Infrared Spectroscopy (FTIR) to determine polymer composition. The majority of the plastic fragments are industrial pellets composed of polypropylene and polyethylene. Varying degrees of oxidation are indicated by multiple irregular peaks in the lower wavenumber region on the FTIR spectra. The oxidized pellets also represent the plastic particles with the most pronounced surface textures, as identified using Scanning Electron Microscopy (SEM). Crazes and flakey, fibrous, or granular textures are consistent with chemical weathering processes, whereas gauges and pits occur through abrasion during mechanical weathering. Further textural and compositional analysis will indicate which polymer types are more resistant to weathering processes. Additional investigation of the distribution of plastic debris along the beaches of Lake Huron will indicate the amount and primary transport directions of resistant plastic debris polluting one of Ontario's Great Lakes.
Impacts of discarded plastic bags on marine assemblages and ecosystem functioning.
Green, Dannielle Senga; Boots, Bas; Blockley, David James; Rocha, Carlos; Thompson, Richard
2015-05-05
The accumulation of plastic debris is a global environmental problem due to its durability, persistence, and abundance. Although effects of plastic debris on individual marine organisms, particularly mammals and birds, have been extensively documented (e.g., entanglement and choking), very little is known about effects on assemblages and consequences for ecosystem functioning. In Europe, around 40% of the plastic items produced are utilized as single-use packaging, which rapidly accumulate in waste management facilities and as litter in the environment. A range of biodegradable plastics have been developed with the aspiration of reducing the persistence of litter; however, their impacts on marine assemblages or ecosystem functioning have never been evaluated. A field experiment was conducted to assess the impact of conventional and biodegradable plastic carrier bags as litter on benthic macro- and meio-faunal assemblages and biogeochemical processes (primary productivity, redox condition, organic matter content, and pore-water nutrients) on an intertidal shore near Dublin, Ireland. After 9 weeks, the presence of either type of bag created anoxic conditions within the sediment along with reduced primary productivity and organic matter and significantly lower abundances of infaunal invertebrates. This indicates that both conventional and biodegradable bags can rapidly alter marine assemblages and the ecosystem services they provide.
Advancing Polymer-Supported Ionogel Electrolytes Formed via Radical Polymerization
NASA Astrophysics Data System (ADS)
Visentin, Adam F.
Applications ranging from consumer electronics to the electric grid have placed demands on current energy storage technologies. There is a drive for devices that store more energy for rapid consumption in the case of electric cars and the power grid, and safer, versatile design options for consumer electronics. Electrochemical double-layer capacitors (EDLCs) are an option that has garnered attention as a means to address these varied energy storage demands. EDLCs utilize charge separation in electrolytes to store energy. This energy storage mechanism allows for greater power density (W kg -1) than batteries and higher energy density (Wh kg-1) than conventional capacitors - along with a robust lifetime in the range of thousands to millions of charge-discharge cycles. Safety and working voltage windows of EDLCs currently on the market are limited by the organic solvents utilized in the electrolyte. A potential solution lies in the replacement of the organic solvents with ionic liquids, or room-temperature molten salts. Ionic liquids possess many superior properties in comparison to conventional solvents: wide electrochemical window, low volatility, nonflammability, and favorable ionic conductivity. It has been an endeavor of this work to exploit these advantages while altering the liquid form factor into a gel. An ionic liquid/solid support scaffold composite electrolyte, or ionogel, adds additional benefits: flexible device design, lower encapsulation weight, and elimination of electrolyte leakage. This work has focused on investigations of a UV-polymerizable monomer, poly(ethylene glycol) diacrylate, as a precursor for forming ionogels in situ. The trade-off between gaining mechanical stability at the cost of ionic conductivity has been investigated for numerous ionogel systems. While gaining a greater understanding of the interactions between the gel scaffold and ionic liquid, an ionogel with the highest known ionic conductivity to date (13.1 mS cm-1) was fabricated. In addition to developing an understanding of UV-polymerized systems, a rapid 10 to 20 second, microwave-assisted polymerization method was developed as a novel means to create ionogels. These ionogels exhibited comparable mechanical response and ionic conductivity levels to those gels fabricated by the UV method. Lastly, an EDLC prototype was fabricated using a UV-polymerized ionogel formed in situ between two high-surface area carbon electrodes. The device performance metrics were comparable to commercial EDLCs, and functioned for several thousand cycles with limited loss in capacitance.
Aerial sampling of emissions from biomass pile burns in ...
Emissions from burning piles of post-harvest timber slash in Grande Ronde, Oregon were sampled using an instrument platform lofted into the plume using a tether-controlled aerostat or balloon. Emissions of carbon monoxide, carbon dioxide, methane, particulate matter (PM2.5 µm), black carbon, ultraviolet absorbing PM, elemental/organic carbon, semi-volatile organics (polycyclic aromatic hydrocarbons and polychlorinated dibenzodioxins/dibenzofurans), filter-based metals, and volatile organics were sampled for determination of emission factors. The effect on emissions from covering or not covering piles with polyethylene sheets to prevent fuel wetting was determined. Results showed that the uncovered (“wet”) piles burned with lower combustion efficiency and higher emissions of volatile organic compounds. Results for other pollutants will also be discussed. This work determined the emissions from open burning of forest slash wood, with and without plastic sheeting. The foresters advocate the use of plastic to keep the slash wood dry and aid in the controlled combustion of the slash to reduce fuel loading. Concerns about the emissions from the burning plastic prompted this work which conducted an extensive characterization of dry, wet, and dry with plastic slash pile emissions.
Nauendorf, Alice; Krause, Stefan; Bigalke, Nikolaus K; Gorb, Elena V; Gorb, Stanislav N; Haeckel, Matthias; Wahl, Martin; Treude, Tina
2016-02-15
To date, the longevity of plastic litter at the sea floor is poorly constrained. The present study compares colonization and biodegradation of plastic bags by aerobic and anaerobic benthic microbes in temperate fine-grained organic-rich marine sediments. Samples of polyethylene and biodegradable plastic carrier bags were incubated in natural oxic and anoxic sediments from Eckernförde Bay (Western Baltic Sea) for 98 days. Analyses included (1) microbial colonization rates on the bags, (2) examination of the surface structure, wettability, and chemistry, and (3) mass loss of the samples during incubation. On average, biodegradable plastic bags were colonized five times higher by aerobic and eight times higher by anaerobic microbes than polyethylene bags. Both types of bags showed no sign of biodegradation during this study. Therefore, marine sediment in temperate coastal zones may represent a long-term sink for plastic litter and also supposedly compostable material. Copyright © 2016 Elsevier Ltd. All rights reserved.
Kühn, Susanne; van Werven, Bernike; van Oyen, Albert; Meijboom, André; Bravo Rebolledo, Elisa L; van Franeker, Jan A
2017-02-15
In studies of plastic ingestion by marine wildlife, visual separation of plastic particles from gastrointestinal tracts or their dietary content can be challenging. Earlier studies have used solutions to dissolve organic materials leaving synthetic particles unaffected. However, insufficient tests have been conducted to ensure that different categories of consumer products partly degraded in the environment and/or in gastrointestinal tracts were not affected. In this study 63 synthetic materials and 11 other dietary items and non-plastic marine debris were tested. Irrespective of shape or preceding environmental history, most polymers resisted potassium hydroxide (KOH) solution, with the exceptions of cellulose acetate from cigarette filters, some biodegradable plastics and a single polyethylene sheet. Exposure of hard diet components and other marine debris showed variable results. In conclusion, the results confirm that usage of KOH solutions can be a useful approach in general quantitative studies of plastic ingestion by marine wildlife. Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.
Brecher, M E; Hay, S N; Rothenberg, S J
2004-03-01
A microbial detection system (BacT/ALERT 3D, bioMérieux [formerly Organon Teknika]) has previously been validated with a variety of bacterial contaminants in PLTs. The recovery of nine organisms seeded into PLTs with new plastic culture bottles was studied in comparison to the current glass bottles. The use of plastic instead of glass would be expected to reduce the risk of injury. Isolates of Bacillus cereus, Enterobacter cloacae, Escherichia coli, Klebsiella pneumoniae, Staphylococcus aureus, Staphylococcus epidermidis, Serratia marcescens, Streptococcus viridans, and Propionibacterium acnes were inoculated into Day 2 (>24 hr <48 hr) apheresis PLT units to 10 and 100 CFUs per mL. Replicate samples (4 mL) were inoculated into both current- and new-generation standard aerobic and anaerobic bottles. All organisms (with the exception of P. acnes) were detected in a mean time of 9.3 to 18.9 hours (10 CFUs/mL) or 8.7 to 18.2 hours (100 CFUs/mL). In aggregate (with the exception of P. acnes), the plastic and glass aerobic bottles had a mean difference in detection of 1.2 hours (p < 0.0001), and the plastic and glass anaerobic bottles had a mean difference of 3.3 hours (p < 0.0001). In all cases, the mean detection time was superior or clinically comparable (within 0.1 hr) with the new plastic bottles. P. acnes (an anaerobic organism) was detected with the new and current anaerobic bottles in a mean of 72.8 and 90.4 hours (10 CFUs/mL) or 64.0 and 80.8 hours (100 CFUs/mL), respectively. The narrower bottle neck and smaller inoculation septum present with the new-generation plastic bottles were inoculated with comparable ease to that of the glass bottles. These data demonstrate that the new plastic bottles are clinically comparable or superior to the current glass standard aerobic and anaerobic culture bottles.
Ferreira, L A; Chervenak, A; Placko, S; Kestranek, A; Madeira, P P; Zaslavsky, B Y
2014-11-14
Solubilities of 17 polar organic compounds in aqueous solutions of Na2SO4, NaCl, NaClO4, and NaSCN at the salt concentrations of up to 1.0-2.0 M were determined and the Setschenow constant, ksalt, values were estimated. It was found that NaClO4 may display both salting-in and salting-out effects depending on the particular compound structure. The Setschenow constant values for all the polar compounds examined in different salt solutions are found to be interrelated. Similar relationships were observed for partition coefficients of nonionic organic compounds in aqueous polyethylene glycol-sodium sulfate two-phase systems in the presence of different salt additives reported previously [Ferreira et al., J. Chromatogr. A, 2011, 1218, 5031], and for the effects of different salts on optical rotation of amino acids reported by Rossi et al. [J. Phys. Chem. B, 2007, 111, 10510]. In order to explain the observed relationships it is suggested that all the effects observed originate as responses of the compounds to the presence of a given ionic environment and its interaction with the compounds by forming direct or solvent-separated ionic pairs. The response is compound-specific and its strength is determined by the compound structure and the type (and concentration) of ions inducing the response.
Li, Jiangsheng; Duan, Chenghao; Wang, Ning; Zhao, Chengjie; Han, Wei; Jiang, Li; Wang, Jizheng; Zhao, Yingjie; Huang, Changshui; Jiu, Tonggang
2018-05-08
The molecular structure of cathode interface modification materials can affect the surface morphology of the active layer and key electron transfer processes occurring at the interface of polymer solar cells in inverted structures mostly due to the change of molecular configuration. To investigate the effects of spatial configuration of the cathode interfacial modification layer on polymer solar cells device performances, we introduced two novel organic ionic salts (linear NS2 and three-dimensional (3D) NS4) combined with the ZnO film to fabricate highly efficient inverted solar cells. Both organic ionic salts successfully decreased the surface traps of the ZnO film and made its work function more compatible. Especially NS4 in three-dimensional configuration increased the electron mobility and extraction efficiency of the interfacial film, leading to a significant improvement of device performance. Power conversion efficiency (PCE) of 10.09% based on NS4 was achieved. Moreover, 3D interfacial modification could retain about 92% of its initial PCE over 160 days. It is proposed that 3D interfacial modification retards the element penetration-induced degradation without impeding the electron transfer from the active layer to the ZnO film, which significantly improves device stability. This indicates that inserting three-dimensional organic ionic salt is an efficient strategy to enhance device performance.
NASA Astrophysics Data System (ADS)
Ueda, Hiroyuki; Takeuchi, Keita; Kikuchi, Akihiko
2018-04-01
We report an organic single crystal growth technique, which uses a nonvolatile liquid thin film as a crystal growth field and supplies fine droplets containing solute from the surface of the liquid thin film uniformly and continuously by electrospray deposition. Here, we investigated the relationships between the solute concentration of the supplied solution and the morphology and size of precipitated crystals for four types of fluorescent organic low molecule material [tris(8-hydroxyquinoline)aluminum (Alq3), 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (PBD), N,N‧-bis(3-methylphenyl)-N,N‧-diphenylbenzidine (TPD), and N,N-bis(naphthalene-1-yl)-N,N-diphenyl-benzidine (NPB)] using an ionic liquid as the nonvolatile liquid. As the concentration of the supplied solution decreased, the morphology of precipitated crystals changed from dendritic or leaf shape to platelike one. At the solution concentration of 0.1 mg/ml, relatively large platelike single crystals with a diagonal length of over 100 µm were obtained for all types of material. In the experiment using ionic liquid and dioctyl sebacate as nonvolatile liquids, it was confirmed that there is a clear positive correlation between the maximum volume of the precipitated single crystal and the solubility of solute under the same solution supply conditions.
Kah, Melanie; Sigmund, Gabriel; Xiao, Feng; Hofmann, Thilo
2017-11-01
The sorption of ionic and ionizable organic compounds (IOCs) (e.g., pharmaceuticals and pesticides) on carbonaceous materials plays an important role in governing the fate, transport and bioavailability of IOCs. The paradigms previously established for the sorption of neutral organic compounds do not always apply to IOCs and the importance of accounting for the particular sorption behavior of IOCs is being increasingly recognized. This review presents the current state of knowledge and summarizes the recent advances on the sorption of IOCs to carbonaceous sorbents. A broad range of sorbents were considered to evaluate the possibility to read across between fields of research that are often considered in isolation (e.g., carbon nanotubes, graphene, biochar, and activated carbon). Mechanisms relevant to IOCs sorption on carbonaceous sorbents are discussed and critically evaluated, with special attention being given to emerging sorption mechanisms including low-barrier, charge-assisted hydrogen bonds and cation-π assisted π-π interactions. The key role played by some environmental factors is also discussed, with a particular focus on pH and ionic strength. Overall the review reveals significant advances in our understanding of the interactions between IOCs and carbonaceous sorbents. In addition, knowledge gaps are identified and priorities for future research are suggested. Copyright © 2017 Elsevier Ltd. All rights reserved.
Volatile organic compounds of polyethylene vinyl acetate plastic are toxic to living organisms.
Meng, Tingzhu Teresa
2014-01-01
Volatile organic compounds (VOCs) in polyvinyl chloride (PVC) plastic products readily evaporate; as a result, hazardous gases enter the ecosystem, and cause cancer in humans and other animals. Polyethylene vinyl acetate (PEVA) plastic has recently become a popular alternative to PVC since it is chlorine-free. In order to determine whether PEVA is harmful to humans, this research employed the freshwater oligochaete Lumbriculus variegatus as a model to compare their oxygen intakes while they were exposed to the original stock solutions of PEVA, PVC or distilled water at a different length of time for one day, four days or eight days. During the exposure periods, the oxygen intakes in both PEVA and PVC groups were much higher than in the distilled water group, indicating that VOCs in both PEVA and PVC were toxins that stressed L. variegatus. Furthermore, none of the worms fully recovered during the24-hr recovery period. Additionally, the L. variegatus did not clump together tightly after four or eight days' exposure to either of the two types of plastic solutions, which meant that both PEVA and PVC negatively affected the social behaviors of these blackworms. The LD50 tests also supported the observations above. For the first time, our results have shown that PEVA plastic has adverse effects on living organisms, and therefore it is not a safe alternative to PVC. Further studies should identify specific compounds causing the adverse effects, and determine whether toxic effect occurs in more complex organisms, especially humans.
NASA Astrophysics Data System (ADS)
Rasyid, B.; Oda, M.; Omae, H.
2018-05-01
Soil-water and plant growth interaction is a primary key to develop environmental plant production system. The objective of this research is to evaluate change in soil water retention characteristics and plant response as the effect of continuous organic matter and plastic mulch application. The experiment was conducted in the plastic house field with plot size of 5 m (length) x 1 m (width). The field had treatments of plastic mulch type (mesh and poly) and no mulch, nitrogen (0, 10 and 40 kg N ha-1), and 2 ton ha-1 organic matter (incorporated into all plots). Water retention measurement using sand box method for low suction and pressure plate apparatus was applied for high suction. Completely randomized block experimental design and Duncan-MRT were used to analysis the effect of treatment on the parameters. Soil organic carbon and nitrogen increased slightly in both mulch types, but C:N ratio decreased in poly mulch which had the lowest value during two planting season. Various change in soil water retention was shown in different mulch type with mesh mulch had the highest result on lower suction, and control was the lowest water retention on the high suction. Soil water availability was highest in mesh mulch type followed by control and poly mulch type. This study could conclude that continuous incorporation of organic matter and mesh-plastic mulch was useful in achieving environments to improve soil C:N ratio and soil water retention.
Elastic resistance change and action potential generation of non-faradaic Pt/TiO2/Pt capacitors.
Lim, Hyungkwang; Jang, Ho Won; Lee, Doh-Kwon; Kim, Inho; Hwang, Cheol Seong; Jeong, Doo Seok
2013-07-21
Electric current in the mixed ionic-electronic conductor TiO2 is hysteretic, i.e. history-dependent, and its use is versatile in electronic devices. Nowadays, biologically inspired, analogue-type computing systems, known as neuromorphic systems, are being actively investigated owing to their new and intriguing physical concepts. The realization of artificial synapses is important for constructing neuromorphic systems. In mammalians' brains, the plasticity of synapses between neighbouring nerve cells arises from action potential firing. Emulating action potential firing via inorganic systems has therefore become important in neuromorphic engineering. In this work, the current-voltage hysteresis of TiO2-based non-faradaic capacitors is investigated to primarily focus on the correlation between the blocking contact and the elasticity, i.e. non-plasticity, of the capacitors' resistance change, in experimental and theoretical methods. The similarity between the action potential firing behaviour in nerve cells and the elasticity of the non-faradaic capacitors is addressed.
Recent progress on thin-film encapsulation technologies for organic electronic devices
NASA Astrophysics Data System (ADS)
Yu, Duan; Yang, Yong-Qiang; Chen, Zheng; Tao, Ye; Liu, Yun-Fei
2016-03-01
Among the advanced electronic devices, flexible organic electronic devices with rapid development are the most promising technologies to customers and industries. Organic thin films accommodate low-cost fabrication and can exploit diverse molecules in inexpensive plastic light emitting diodes, plastic solar cells, and even plastic lasers. These properties may ultimately enable organic materials for practical applications in industry. However, the stability of organic electronic devices still remains a big challenge, because of the difficulty in fabricating commercial products with flexibility. These organic materials can be protected using substrates and barriers such as glass and metal; however, this results in a rigid device and does not satisfy the applications demanding flexible devices. Plastic substrates and transparent flexible encapsulation barriers are other possible alternatives; however, these offer little protection to oxygen and water, thus rapidly degrading the devices. Thin-film encapsulation (TFE) technology is most effective in preventing water vapor and oxygen permeation into the flexible devices. Because of these (and other) reasons, there has been an intense interest in developing transparent barrier materials with much lower permeabilities, and their market is expected to reach over 550 million by 2025. In this study, the degradation mechanism of organic electronic devices is reviewed. To increase the stability of devices in air, several TFE technologies were applied to provide efficient barrier performance. In this review, the degradation mechanism of organic electronic devices, permeation rate measurement, traditional encapsulation technologies, and TFE technologies are presented.
Su, Rui; Li, Dan; Wu, Lijie; Han, Jing; Lian, Wenhui; Wang, Keren; Yang, Hongmei
2017-07-01
A novel microextraction method, termed microwave-assisted ionic liquid/ionic liquid dispersive liquid-liquid microextraction, has been developed for the rapid enrichment and analysis of triazine herbicides in fruit juice samples by high-performance liquid chromatography. Instead of using hazardous organic solvents, two kinds of ionic liquids, a hydrophobic ionic liquid (1-hexyl-3-methylimidazolium hexafluorophosphate) and a hydrophilic ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate), were used as the extraction solvent and dispersion agent, respectively, in this method. The extraction procedure was induced by the formation of cloudy solution, which was composed of fine drops of 1-hexyl-3-methylimidazolium hexafluorophosphate dispersed entirely into sample solution with the help of 1-butyl-3-methylimidazolium tetrafluoroborate. In addition, an ion-pairing agent (NH 4 PF 6 ) was introduced to improve recoveries of the ionic liquid phase. Several experimental parameters that might affect the extraction efficiency were investigated. Under the optimum experimental conditions, the linearity for determining the analytes was in the range of 5.00-250.00 μg/L, with the correlation coefficients of 0.9982-0.9997. The practical application of this effective and green method is demonstrated by the successful analysis of triazine herbicides in four juice samples, with satisfactory recoveries (76.7-105.7%) and relative standard deviations (lower than 6.6%). In general, this method is fast, effective, and robust to determine triazine herbicides in juice samples. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Compositions of volatile organic compounds emitted from melted virgin and waste plastic pellets.
Yamashita, Kyoko; Yamamoto, Naomichi; Mizukoshi, Atsushi; Noguchi, Miyuki; Ni, Yueyong; Yanagisawa, Yukio
2009-03-01
To characterize potential air pollution issues related to recycling facilities of waste plastics, volatile organic compounds (VOCs) emitted from melted virgin and waste plastics pellets were analyzed. In this study, laboratory experiments were performed to melt virgin and waste plastic pellets under various temperatures (150, 200, and 250 degrees C) and atmospheres (air and nitrogen [N2]). In the study presented here, low-density polyethylene (LDPE), polypropylene (PP), polystyrene (PS) and the recycled waste plastic pellets were used. The VOCs generated from each plastic pellets were collected by Tenax/Carboxen adsorbent tubes and analyzed by thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS). The result showed the higher temperatures generated larger amounts of total VOCs (TVOCs). The VOCs emitted from the virgin plastic pellets likely originated from polymer degradation. Smaller TVOC emissions were observed in N2 atmosphere than in air atmosphere. In particular, larger amounts of the oxygenated compounds, which are generally hazardous and malodorous, were detected in air than in N2. In addition to the compounds originating from polymer degradation, the compounds originating from the plastic additives were also detected from LDPE and PS. Furthermore, various species of VOCs likely originating from contaminant inseparate polyvinyl chloride (PVC), food residues, cleaning agents, degreasers, and so on were detected from the waste plastic. Thus, melting waste plastics, as is conducted in recycling facilities, might generate larger amounts of potentially toxic compounds than producing virgin plastics.
NASA Astrophysics Data System (ADS)
Lian, Cheng; Liu, Honglai; Henderson, Douglas; Wu, Jianzhong
2016-10-01
The ionophobicity effect of nanoporous electrodes on the capacitance and the energy storage capacity of nonaqueous-electrolyte supercapacitors is studied by means of the classical density functional theory (DFT). It has been hypothesized that ionophobic nanopores may create obstacles in charging, but they store energy much more efficiently than ionophilic pores. In this study, we find that, for both ionic liquids and organic electrolytes, an ionophobic pore exhibits a charging behavior different from that of an ionophilic pore, and that the capacitance-voltage curve changes from a bell shape to a two-hump camel shape when the pore ionophobicity increases. For electric-double-layer capacitors containing organic electrolytes, an increase in the ionophobicity of the nanopores leads to a higher capacity for energy storage. Without taking into account the effects of background screening, the DFT predicts that an ionophobic pore containing an ionic liquid does not enhance the supercapacitor performance within the practical voltage ranges. However, by using an effective dielectric constant to account for ion polarizability, the DFT predicts that, like an organic electrolyte, an ionophobic pore with an ionic liquid is also able to increase the energy stored when the electrode voltage is beyond a certain value. We find that the critical voltage for an enhanced capacitance in an ionic liquid is larger than that in an organic electrolyte. Our theoretical predictions provide further understanding of how chemical modification of porous electrodes affects the performance of supercapacitors. The authors are saddened by the passing of George Stell but are pleased to contribute this article in his memory. Some years ago, DH gave a talk at a Gordon Conference that contained an approximation that George had demonstrated previously to be in error in one of his publications. Rather than making this point loudly in the discussion, George politely, quietly, and privately pointed this out later. In 2002, DH shared a room with George at a conference in China. This is remembered fondly.
Clothing for use in clean-air environments.
Clark, R. P.; Mullan, B. J.
1976-01-01
Disposable plastic two-piece suits were compared with conventional cotton suits, gowns, and plastic aprons by nurses in a burns unit. The plastic suits allowed fewer micro-organisms to be dispersed into the environment than the other garments but were less comfortable. Images Plate 1 PMID:1068201
METHOD OF USING AND MANUFACTURING PLASTIC EQUIVALENT TO ORGANIC MATERIALS
Shonka, F.R.; Rose, J.E.; Failla, G.
1961-10-24
Compositions of matter that have the radiation response of animal muscle tissue, bone, or air were prepared. These compositions are composed of specific proportions of three or more of the following constituents: polyethylene plastic, polyamide plastic, oil furnace black, silica, and calcium fluoride. (AEC)
Sorption-desorption of fipronil in some soils, as influenced by ionic strength, pH and temperature.
Singh, Anand; Srivastava, Anjana; Srivastava, Prakash C
2016-08-01
The sorption-desorpion of fipronil insecticide is influenced by soil properties and variables such as pH, ionic strength, temperature, etc. A better understanding of soil properties and these variables in sorption-desorption processes by quantification of fipronil using liquid chromatography may help to optimise suitable soil management to reduce contamination of surface and groundwaters. In the present investigation, the sorption-desorption of fipronil was studied in some soils at varying concentrations, ionic strengths, temperatures and pH values, and IR specta of fipronil sorbed onto soils were studied. The sorption of fipronil onto soils conformed to the Freundlich isotherm model. The sorption-desorption of fipronil varied with ionic strength in each of the soils. Sorption decreased but desorption increased with temperature. Sorption did not change with increasing pH, but for desorption there was no correlation. The cumulative desorption of fipronil from soil was significantly and inversely related to soil organic carbon content. IR spectra of sorbed fipronil showed the involvement of amino, nitrile, sulfone, chloro and fluoro groups and the pyrazole nucleus of the fipronil molecule. The sorption of fipronil onto soils appeared to be a physical process with the involvement of hydrogen bonding. An increase in soil organic carbon may help to reduce desorption of fipronil. High-temperature regimes are more conducive to the desorption. © 2015 Society of Chemical Industry. © 2015 Society of Chemical Industry.
NASA Astrophysics Data System (ADS)
Mekic, Majda; Brigante, Marcello; Vione, Davide; Gligorovski, Sasho
2018-07-01
There is increasing evidence that aqueous-phase atmospheric chemistry is an important source of secondary organic aerosols (SOA), but the related processes are currently not adequately represented in atmospheric chemistry models. Here we show that the absorption spectrum of pyruvic acid (PA) exhibits both an increase of the absorption intensity and a red shift of 13 nm while going from a dilute aqueous phase to a solution containing the inert salt sodium perchlorate (5M NaClO4). If this phenomenon turns out to be more general, many compounds that do not absorb actinic light in clouds and fog could become light absorbers at elevated salt concentrations in aerosol deliquescent particles. Compared to the direct photolysis of PA in dilute aqueous solution, the photolysis rate is increased by three times at high ionic strength (5M NaClO4). Such a considerable enhancement can be rationalized in the framework of the Debye-McAulay approach for reactions of ionic + neutral (or neutral + neutral) species, considering that the PA direct photolysis likely involves interaction between the photogenerated triplet state and water. This is, to our knowledge, the first report of a significant effect of the ionic strength on the rate of an atmospheric photochemical reaction. The phenomenon has important implications for the fate of PA and, potentially, of other organic compounds in atmospheric aerosol deliquescent particles.
Peng, Cheng; Shen, Chensi; Zheng, Siyuan; Yang, Weiling; Hu, Hang; Liu, Jianshe; Shi, Jiyan
2017-01-01
Many studies have shown the effect of solution chemistry on the environmental behavior of metal-based nanoparticles (NPs), except CuO NPs. Here, we investigated the agglomeration, sedimentation, dissolution, and speciation of CuO NPs by varying pH, ionic strength, ionic valence, and natural organic matter (NOM). The results showed that as the pH moved away from 6, the size of CuO agglomerates decreased, along with the enhanced NP suspension stabilization, due to the increase of electrostatic repulsive force. Increasing ionic strength and valence intensified the agglomeration and sedimentation of CuO NPs because of the compression of electrical double layers. The presence of humic acid and citric acid enhanced the dispersion and stabilization of CuO NP suspension, but l-cysteine showed a different impact. Decreasing pH, increasing ionic strength and all NOM improved the dissolution of CuO NPs, but the divalent electrolyte (CaCl2) inhibited the Cu2+ release from CuO NPs compared to the monovalent electrolyte (NaCl). In addition, X-ray absorption near edge structure (XANES) analysis demonstrated that the presence of l-cysteine transformed more than 30% of CuO NPs to Cu(I)-cysteine by coordinating with thiol group. This study can give us an in-depth understanding on the environmental behavior and fate of CuO NPs in the aquatic environment. PMID:29036921
Solid polymer electrolyte compositions
Garbe, James E.; Atanasoski, Radoslav; Hamrock, Steven J.; Le, Dinh Ba
2001-01-01
An electrolyte composition is featured that includes a solid, ionically conductive polymer, organically modified oxide particles that include organic groups covalently bonded to the oxide particles, and an alkali metal salt. The electrolyte composition is free of lithiated zeolite. The invention also features cells that incorporate the electrolyte composition.
Method of making ionic liquid mediated sol-gel sorbents
Malik, Abdul; Shearrow, Anne M.
2017-01-31
Ionic liquid (IL)-mediated sol-gel hybrid organic-inorganic materials present enormous potential for effective use in analytical microextraction. One obstacle to materializing this prospect arises from high viscosity of ILs significantly slowing down sol-gel reactions. A method was developed which provides phosphonium-based, pyridinium-based, and imidazolium-based IL-mediated advanced sol-gel organic-inorganic hybrid materials for capillary microextraction. Scanning electron microscopy results demonstrate that ILs can serve as porogenic agents in sol-gel reactions. IL-mediated sol-gel coatings prepared with silanol-terminated polymers provided up to 28 times higher extractions compared to analogous sol-gel coatings prepared without any IL in the sol solution. This study shows that IL-generated porous morphology alone is not enough to provide effective extraction media: careful choice of the organic polymer and the precursor with close sol-gel reactivity must be made to ensure effective chemical bonding of the organic polymer to the created sol-gel material to be able to provide the desired sorbent characteristics.
Understanding ion association states and molecular dynamics using infrared spectroscopy
NASA Astrophysics Data System (ADS)
Masser, Hanqing
A molecular level understanding of the ion transport mechanism within polymer electrolytes is crucial to the further development for advanced energy storage applications. This can be achieved by the identification and quantitative measurement of different ion species in the system and further relating them to the ion conductivity. In the first part of this thesis, research is presented towards understanding the ion association states (free ions, ion pairs and ion aggregates) in ionomer systems, and the correlation of ion association states, ion conduction, polymer dynamics, and morphology. Ion conductivity in ionomers can be improved by lowering glass transition temperature, increasing polymer ion solvation ability, and adjusting ionomer structural variables such as ion content, cation type and side chain structure. These effects are studied in three ionomer systems respectively, using a combination of characterization methods. Fourier Transform Infrared Spectroscopy (FTIR) identifies and quantifies the ion association states. Dielectric Spectroscopy (DRS) characterizes ion conductivity and polymer and ion dynamics. X-ray scattering reveals changes in morphology. The influence of a cation solvating plasticizer on a polyester ionomer is systematically investigated with respect to ion association states, ion and polymer dynamics and morphology. A decrease in the number ratio of ion aggregates with increased plasticizer content and a slight increase at elevated temperature are observed in FTIR. Similar results are also detected by X-ray scattering. As determined from dielectric spectroscopy, ion conductivity increases with plasticizer content, in accordance with the decrease in glass transition temperature. Research on copolymer of poly(ethylene oxide) (PEO) and poly(tetramethylene oxide) (PTMO) based ionomers further develops an understanding of the trade-off between ion solvation and segmental dynamics. Upon the incorporation of PTMO, the majority of the PTMO microphase separates from the PEO-rich microphase, and ionic groups are preferentially solvated by PEO chains and reside in the PEO-rich microphase. As the ratio of PTMO increases, the fraction of aggregates increases, resulting in more highly coordinated aggregation states. Results on ion association states are in good agreement with previous results on ion conductivity, polymer dynamics and morphology. The effects of ion content, cation type and ionic side chain structure on ion association states are systemically studied in a series of ionomers with short ethylene oxide and ionic sulfonated styrene side chains, and then correlated to the ion and polymer dynamic characterization. It is found that ionomers with modest ion content, large cation and styrene ionic side chain have the most "free ions" and ion pairs, and highest ion conductivity. Ion conduction in ionomers is optimized by systematically changing their chemical structures. In addition to knowledge of ion association states, a IR band shape also contains information on molecular dynamics. In companion investigation, the vibrational relaxation and dynamic transitions of conformationally insensitive normal modes in two different polymer systems (atactic polystyrene and deuterated poly(methyl methacrylate)) are studied. The information on vibrational relaxations is resolved by conducting precisely controlled FTIR experiments, applying specialized curve resolving data analysis, and calculating time correlation functions through numerical Fourier transformation. The vibrational relaxations of these modes can be described by a two process model: a fast process on the time scale of 0.01 ps, which is inhomogeneously broadened by a slow process on the time scale of picoseconds.
Plastic ingestion by Scyliorhinus canicula trawl captured in the North Sea.
Smith, L E
2018-05-01
The ingestion of plastic debris by marine organisms has been documented across a variety of taxa including; marine mammals, sea birds, sea turtles and some fish species. Fewer reports have described ingestion by sharks, in this study the gastrointestinal tracts of 20 small spotted catsharks (Scyliorhinus canicula) trawl captured in the North Sea were investigated. Macroplastics (>20 mm) were found in 2 individuals and microplastic (<5 mm) was found in one other individual, this is the first time that plastic ingestion has been reported in this species. These observations suggest that gastrointestinal analysis of commonly landed elasmobranch species is worthwhile, to further understanding on the organisms and habitats impacted by plastic pollution. Copyright © 2018 Elsevier Ltd. All rights reserved.
Krenz, Wulf-Dieter C.; Parker, Anna R.; Rodgers, Edmund W.; Baro, Deborah J.
2014-01-01
Long-term intrinsic and synaptic plasticity must be coordinated to ensure stability and flexibility in neuronal circuits. Coordination might be achieved through shared transduction components. Dopamine (DA) is a well-established participant in many forms of long-term synaptic plasticity. Recent work indicates that DA is also involved in both activity-dependent and -independent forms of long-term intrinsic plasticity. We previously examined DA-enabled long-term intrinsic plasticity in a single identified neuron. The lateral pyloric (LP) neuron is a component of the pyloric network in the crustacean stomatogastric nervous system (STNS). LP expresses type 1 DA receptors (D1Rs). A 1 h bath application of 5 nM DA followed by washout produced a significant increase in the maximal conductance (Gmax) of the LP transient potassium current (IA) that peaked ~4 h after the start of DA application; furthermore, if a change in neuronal activity accompanied the DA application, then a persistent increase in the LP hyperpolarization activated current (Ih) was also observed. Here, we repeated these experiments with pharmacological and peptide inhibitors to determine the cellular processes and signaling proteins involved. We discovered that the persistent, DA-induced activity-independent (IA) and activity-dependent (Ih) changes in ionic conductances depended upon many of the same elements that enable long-term synaptic plasticity, including: the D1R-protein kinase A (PKA) axis, RNA polymerase II transcription, RNA interference (RNAi), and mechanistic target of rapamycin (mTOR)-dependent translation. We interpret the data to mean that increasing the tonic DA concentration enhances expression of a microRNA(s) (miRs), resulting in increased cap-dependent translation of an unidentified protein(s). PMID:24596543
Kobayashi, Daigo; Fujita, Kyoko; Nakamura, Nobuhumi; Ohno, Hiroyuki
2015-02-01
Here, we proposed a simple recovery process for poly(3-hydroxybutyrate) (PHB) accumulated in cyanobacteria by using ionic liquids (ILs), which dissolve cyanobacteria but not PHB. First, we investigated the effects of IL polarity on hydrogen-bonding receipt ability (β value) and hydrogen-bonding donating ability (α value) and evaluated the subsequent dissolution of cyanobacteria. We found that ILs having α values higher than approximately 0.4 and β values of approximately 0.9 were suitable for dissolution of cyanobacteria. In particular, 1-ethyl-3-methylimidazolium methylphosphonate ([C2mim][MeO(H)PO2]) was found to dissolve cyanobacteria components, but not PHB. Thus, we verified that PHB produced in cyanobacteria could be separated and recovered by simple filtering after dissolution of cyanobacteria in [C2mim][MeO(H)PO2]. Using this technique, more than 98 % of PHB was obtained on the filter as residues separated from cyanobacteria. Furthermore, [C2mim][MeO(H)PO2] maintained the ability to dissolve cyanobacteria after a simple recycling procedure.
NASA Astrophysics Data System (ADS)
Lan, Xin; Bai, Lu; Li, Xin; Ma, Shuang; He, Xiaozhi; Meng, Fanbao
2014-10-01
Cholesteryl-containing ionic liquid crystals (ILCs) 1-cholesteryloxycarbonylmethyl(propyl)-3-methyl(butyl)imidazolium chlorides ([Ca-Me-Im]Cl, [Ca-Bu-Im]Cl, [Cb-Me-Im]Cl and [Cb-Bu-Im]Cl) and corresponding imidazolium tetrachloroaluminates ([Ca-Me-Im]AlCl4, [Ca-Bu-Im]AlCl4, [Cb-Me-Im]AlCl4 and [Cb-Bu-Im]AlCl4) were synthesized in this work, and the chemical structure, LC behavior and ionic conductivity of all these ILCs were characterized by several technical methods. The imidazolium-based salts with Cl- ions showed chiral smectic A (SA*) phase on both heating and cooling cycles, while the tetrachloroaluminates exhibited chiral nematic (N*) phase. The mesophase was confirmed by characteristic LC textures observed by polarizing optical microscopy and typical diffractogram obtained by X-ray diffraction measurements. The samples with similar cholesteryl-linkage component showed similar phase transition temperature and entropy, indicating the cholesteryl component influence predominately on the phase transition rather than alkyl substituents on the imidazole ring. The imidazolium tetrachloroaluminates display relatively low phase transition temperature compared with the precursor chlorides. The functional difference in LC behavior and ionic conductivity were discussed by investigated the structural difference between the Cl--containing and AlCl4-containing materials. The imidazolium chlorides exhibited layer structure both in crystal and mesophase states, and should be organized with a ‘head-to-tail’ organization to form interdigitated monolayer structures due to the tight ion pairs. But the imidazolium tetrachloroaluminates displayed layer structure only in crystal phase, and should be organized in ‘head-to-head’ arrangements form bilayer structures due to loose combination of ion pairs despite of hydrogen-bond and electrostatic attraction interaction.
You, Xiangwei; Chen, Xiaochu; Liu, Fengmao; Hou, Fan; Li, Yiqiang
2018-01-15
A novel and simple ionic liquid-based air-assisted liquid-liquid microextraction technique combined with high performance liquid chromatography was developed to analyze five fungicides in juice samples. In this method, ionic liquid was used instead of a volatile organic solvent as the extraction solvent. The emulsion was formed by pulling in and pushing out the mixture of aqueous sample solution and extraction solvent repeatedly using a 10mL glass syringe. No organic dispersive solvent was required. Under the optimized conditions, the limits of detection (LODs) were 0.4-1.8μgL -1 at a signal-to-noise ratio of 3. The limits of quantification (LOQs) set as the lowest spiking levels with acceptable recovery in juices were 10μgL -1 , except for fludioxonil whose LOQ was 20μgL -1 . The proposed method was applied to determine the target fungicides in juice samples, and acceptable recoveries ranging from 74.9% to 115.4% were achieved. Copyright © 2017. Published by Elsevier Ltd.
Purification and crystal growth of NPB via imidazolium based ionic liquids
NASA Astrophysics Data System (ADS)
Oh, Yong-Taeg; Shin, Dong-Chan
2018-04-01
Here we report the production of high purity and crystallinity organic electronic material of NPB (N,N‧-Di-[(1-naphthyl)-N,N‧-diphenyl]-1,1‧-biphenyl-4,4‧-diamine (C44H32N2) through solution recrystallization within imidazolium based ionic liquids. When low purity NPB was recrystallized at 170 °C within C8MIM[TFSI], its purity was drastically improved from 82% to 99.92%. These recrystallized NPB crystals showed 0.040° FWHM (Full Width Half Maximum) of X-ray (1 1 1) diffraction peak. Such small FWHM angle indicates single-crystal like crystallinity. Initial NPB powder was dissolved at 100 °C and recrystallized at temperature above 110 °C. At higher temperature of 170 °C, a small number of bigger crystals were formed compared to those at 110 °C. This can be well explained by the classical nucleation and growth theory. Therefore, solution recrystallization process using ionic liquid might be promising for mass production of organic electronic materials by replacing the widely-used sublimation purification method.
Octanol-water distribution of engineered nanomaterials.
Hristovski, Kiril D; Westerhoff, Paul K; Posner, Jonathan D
2011-01-01
The goal of this study was to examine the effects of pH and ionic strength on octanol-water distribution of five model engineered nanomaterials. Distribution experiments resulted in a spectrum of three broadly classified scenarios: distribution in the aqueous phase, distribution in the octanol, and distribution into the octanol-water interface. Two distribution coefficients were derived to describe the distribution of nanoparticles among octanol, water and their interface. The results show that particle surface charge, surface functionalization, and composition, as well as the solvent ionic strength and presence of natural organic matter, dramatically impact this distribution. Distributions of nanoparticles into the interface were significant for nanomaterials that exhibit low surface charge in natural pH ranges. Increased ionic strengths also contributed to increased distributions of nanoparticle into the interface. Similarly to the octanol-water distribution coefficients, which represent a starting point in predicting the environmental fate, bioavailability and transport of organic pollutants, distribution coefficients such as the ones described in this study could help to easily predict the fate, bioavailability, and transport of engineered nanomaterials in the environment.
Arp, H P H; Brown, T N; Berger, U; Hale, S E
2017-07-19
The contaminants that have the greatest chances of appearing in drinking water are those that are mobile enough in the aquatic environment to enter drinking water sources and persistent enough to survive treatment processes. Herein a screening procedure to rank neutral, ionizable and ionic organic compounds for being persistent and mobile organic compounds (PMOCs) is presented and applied to the list of industrial substances registered under the EU REACH legislation as of December 2014. This comprised 5155 identifiable, unique organic structures. The minimum cut-off criteria considered for PMOC classification herein are a freshwater half-life >40 days, which is consistent with the REACH definition of freshwater persistency, and a log D oc < 4.5 between pH 4-10 (where D oc is the organic carbon-water distribution coefficient). Experimental data were given the highest priority, followed by data from an array of available quantitative structure-activity relationships (QSARs), and as a third resort, an original Iterative Fragment Selection (IFS) QSAR. In total, 52% of the unique REACH structures made the minimum criteria to be considered a PMOC, and 21% achieved the highest PMOC ranking (half-life > 40 days, log D oc < 1.0 between pH 4-10). Only 9% of neutral substances received the highest PMOC ranking, compared to 30% of ionizable compounds and 44% of ionic compounds. Predicted hydrolysis products for all REACH parents (contributing 5043 additional structures) were found to have higher PMOC rankings than their parents, due to increased mobility but not persistence. The fewest experimental data available were for ionic compounds; therefore, their ranking is more uncertain than neutral and ionizable compounds. The most sensitive parameter for the PMOC ranking was freshwater persistency, which was also the parameter that QSARs performed the most poorly at predicting. Several prioritized drinking water contaminants in the EU and USA, and other contaminants of concern, were identified as PMOCs. This identification and ranking procedure for PMOCs can be part of a strategy to better identify contaminants that pose a threat to drinking water sources.
Glial diffusion barriers during aging and pathological states.
Syková, E
2001-01-01
In conclusion, glial cells control not only ECS ionic composition, but also ECS size and geometry. Since ECS ionic and volume changes have been shown to play an important role in modulating the complex synaptic and extrasynaptic signal transmission in the CNS, glial cells may thus affect neuronal interaction, synchronization and neuron-glia communication. As shown in Fig. 2, a link between ionic and volume changes and signal transmission has been proposed as a model for the non-specific feedback mechanism suppressing neuronal activity (Syková, 1997; Ransom, 2000). First, neuronal activity results in the accumulation of [K+]e, which in turn depolarizes glial cells, and this depolarization induces an alkaline shift in glial pHi. Second, the glial cells extrude acid and the resulting acid shift causes a decrease in the neuronal excitability. Because ionic transmembrane shifts are always accompanied by water, this feedback mechanism is amplified by activity-related glial swelling compensated for by ECS volume shrinkage and by increased tortuosity, presumably by the crowding of molecules of the ECS matrix and/or by the swelling of fine glial processes. This, in turn, results in a larger accumulation of ions and other neuroactive substances in the brain due to increased diffusion hinderance in the ECS. Astrocyte hypertrophy, proliferation and swelling influence the size of the ECS volume and tortuosity around neurons, slowing diffusion in the ECS. Their organization may also affect diffusion anisotropy, which could be an underlying mechanism for the specificity of extrasynaptic transmission, including 'cross-talk' between distinct synapses (Barbour and Hausser, 1997; Kullmann and Asztely, 1998). An increased concentration of transmitter released into a synapse (e.g. repetitive adequate stimuli or during high frequency electrical stimulation which induces LTP) results in a significant activation of high-affinity receptors at neighboring synapses. The efficacy of such synaptic cross-talk would be dependent on the extracellular space surrounding the synapses, i.e. on intersynaptic geometry and diffusion parameters. Other recent studies have also suggested an important role for proteoglycans, known to participate in multiple cellular processes, such as axonal outgrowth, axonal branching and synaptogenesis (Hardington and Fosang, 1992; Margolis and Margolis, 1993) that are important for the formation of memory traces. Recent observation of a decrease of fibronectin and chondroitin sulfate proteoglycan staining in the hippocampus of behaviorally impaired aged rats (Syková et al., 1998a,b) supports this hypothesis. It is reasonable to assume that besides neuronal and glial processes, macromolecules of the extracellular matrix contribute to diffusion barriers in the ECS. It is therefore apparent that glial cells play an important role in the local architecture of the CNS and they may also be involved in the modulation of signal transmission, in plastic changes, LTP, LTD and in changes of behavior and memory formation.
Applications of aerospace technology in industry, a technology transfer profile: Plastics
NASA Technical Reports Server (NTRS)
1971-01-01
New plastics technology bred out of the space program has moved steadily into the U.S. economy in a variety of organized and deliberate ways. Examples are presented of the transfer of plastics know-how into the plants and eventually the products of American business.
Hybrid Nanowire Ion-to-Electron Transducers for Integrated Bioelectronic Circuitry.
Carrad, D J; Mostert, A B; Ullah, A R; Burke, A M; Joyce, H J; Tan, H H; Jagadish, C; Krogstrup, P; Nygård, J; Meredith, P; Micolich, A P
2017-02-08
A key task in the emerging field of bioelectronics is the transduction between ionic/protonic and electronic signals at high fidelity. This is a considerable challenge since the two carrier types exhibit intrinsically different physics and are best supported by very different materials types-electronic signals in inorganic semiconductors and ionic/protonic signals in organic or bio-organic polymers, gels, or electrolytes. Here we demonstrate a new class of organic-inorganic transducing interface featuring semiconducting nanowires electrostatically gated using a solid proton-transporting hygroscopic polymer. This model platform allows us to study the basic transducing mechanisms as well as deliver high fidelity signal conversion by tapping into and drawing together the best candidates from traditionally disparate realms of electronic materials research. By combining complementary n- and p-type transducers we demonstrate functional logic with significant potential for scaling toward high-density integrated bioelectronic circuitry.
Nakazawa, Akira; Tang, Ning; Inoue, Yoshinori; Kamichatani, Waka; Katoh, Toshifumi; Saito, Mitsuru; Obara, Kenji; Toriba, Akira; Hayakawa, Kazuichi
2017-01-01
Diallylamine-maleic acid copolymer (DAM)-nonwoven fabric (DAM-f), a fibrous adsorbent, contains DAM with zwitter-ionic functional groups and forms a hydration layer on the surface. The aim of this report was to evaluate the adsorption selectivity of DAM-f to semi-volatile organic acid (C1-C5). In the aqueous phase, formic acid dissolved in the hydration layer bound to the imino group of DAM-f due to anion exchange interaction. In the gas phase, the adsorption amounts of organic acids increased with the exposure time. Moreover, the adsorption rate constants correlated with the air/water partition coefficients (log K aw ) for formic acid, propionic acid, butyric acid, valeric acid and isovaleric acid, except for acetic acid. These results indicate that DAM-f is highly selective to hydrophilic compounds which easily move from the air to the hydration layer of DAM-f.
Wu, Cheng-Yeu; Young, David; Martel, Jan; Young, John D
2015-01-01
Analysis of the chemical composition of mineral particles found in the body is critical to understand the formation and effects of these entities in vivo. Yet, the possibility that biological fluids may modulate particle composition over time has not been examined. Materials & methods: Mineralo-organic nanoparticles similar to the ones that spontaneously form in human tissues were analyzed using electron microscopy, spectroscopy and proteomic analyses. We show that the mineralo-organic nanoparticles assimilate various ions and minerals during incubation in ionic solutions simulating body fluids. The particles undergo dissolution-reprecipitation reactions that affect the final protein composition of the particles. The reactions occurring at the mineral-water interface therefore modulate the ionic and organic composition of mineral nanoparticles formed in biological fluids, producing changes that may alter the effects of mineral particles and stones in vivo.
Werner, Justyna
2016-04-01
Task-specific ionic liquid-based ultrasound-assisted dispersive liquid-liquid microextraction was used for the preconcentration of cadmium(II), cobalt(II), and lead(II) ions in tea samples, which were subsequently analyzed by liquid chromatography with UV detection. The proposed method of preconcentration is free of volatile organic compounds, which are often used as extractants and dispersing solvents in classic techniques of microextraction. A task-specific ionic liquid trioctylmethylammonium thiosalicylate was used as an extractant and a chelating agent. Ultrasound was used to disperse the ionic liquid. After microextraction, the phases were separated by centrifugation, and the ionic liquid phase was solubilized in methanol and directly injected into the liquid chromatograph. Selected microextraction parameters, such as the volume of ionic liquid, the pH of the sample, the duration of ultrasound treatment, the speed and time of centrifugation, and the effect of ionic strength, were optimized. Under optimal conditions an enrichment factor of 200 was obtained for each analyte. The limits of detection were 0.002 mg/kg for Cd(II), 0.009 mg/kg for Co(II), and 0.013 mg/kg for Pb(II). The accuracy of the proposed method was evaluated by an analysis of the Certified Reference Materials (INCT-TL-1, INCT-MPH-2) with the recovery values in the range of 90-104%. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Gao, Lichao; McCarthy, Thomas J
2007-10-09
Liquid marbles have been reported during this decade and have been argued to be potentially useful for microfluidic and lab-on-a-chip applications. The liquid marbles described to date have been composed of either water or glycerol as the liquid and hydrophobized lycopodium or silica as the stabilizing particles. Both of these components are potentially reactive and do not permit the use of organic chemistry; the liquids are volatile. We report the use of perfluoroalkyl particles (oligomeric (OTFE) and polymeric (PTFE) tetrafluoroethylene, which are unreactive) to support/stabilize a range of ionic liquid marbles. Ionic liquids are not volatile and have been demonstrated to be versatile solvents for chemical transformations. Water marbles prepared with OTFE are much more robust than those prepared with hydrophobized lycopodium or silica.
NASA Astrophysics Data System (ADS)
Roy, Arpita; Dutta, Rupam; Sarkar, Nilmoni
2016-11-01
The present investigation unravels the effect of trehalose on 1-hexadecyl-3-methylimidazolium chloride ([C16mim]Cl), a cationic surface active ionic liquid (SAIL) micelle and SAIL ([C16mim]Cl)-nonionic surfactant (Sorbitan Stearate, Span 60) based vesicles. The influence of trehalose on size and morphology of the aggregates has been investigated using dynamic light scattering (DLS) and transmission electron microscopic (TEM) measurements. Besides, we have studied the dynamic properties of curcumin inside these aggregates using fluorescence spectroscopic based techniques. The results revealed that trehalose molecules play crucial role in modulation of the photophysical properties of curcumin in these organized assemblies.
Thermal regeneration of an electrochemical concentration cell
Krumpelt, Michael; Bates, John K.
1981-01-01
A system and method for thermally regenerating an electrochemical concentration cell having first and second aluminum electrodes respectively positioned in contact with first and second electrolytes separated by an ion exchange member, the first and second electrolytes being composed of different concentrations of an ionic solvent and a salt, preferably an aluminum halide. The ionic solvent may be either organic or inorganic with a relatively low melting point, the ionic solvent and the salt form a complex wherein the free energy of formation of said complex is less than about -5 Kcal/mole. A distillation column using solar heat or low grade industrial waste heat receives the first and second electrolytes and thermally decomposes the salt-solvent complex to provide feed material for the two half cells.
Yang, Jinjuan; Wei, Hongmin; Teng, Xiane; Zhang, Hanqi; Shi, Yuhua
2014-01-01
Ionic liquids have attracted much attention as an extraction solvent instead of traditional organic solvent in single-drop microextraction. However, non-volatile ionic liquids are difficult to couple with gas chromatography. Thus, the following injection system for the determination of organic compounds is described. To establish an environmentally friendly, simple, and effective extraction method for preparation and analysis of the essential oil from aromatic plants. The dynamic ultrasonic nebulisation extraction was coupled with headspace ionic liquid-based single-drop microextraction(UNE-HS/IL/SDME)for the extraction of essential oils from Forsythia suspense fruits. After 13 min of extraction for 50 mg sample, the extracts in ionic liquid were evaporated rapidly in the gas chromatography injector through a thermal desorption unit (5 s). The traditional extraction method was carried out for comparative study. The optimum conditions were: 3 μL of 1-methyl-3-octylimidazolium hexafluorophosphate was selected as the extraction solvent, the sample amount was 50 mg, the flow rate of purging gas was 200 mL/min, the extraction time was 13 min, the injection volume was 2 μL, and the thermal desorption temperature and time were 240 °C and 5 s respectively. Comparing with hydrodistillation (HD), the proposed method was environment friendly and efficient. The proposed method is environmentally friendly, time saving, with high efficiency and low consumption. It would extend the application range of the HS/SDME and would be useful especially for aromatic plants analysis. Copyright © 2013 John Wiley & Sons, Ltd.
Dussud, C; Meistertzheim, A L; Conan, P; Pujo-Pay, M; George, M; Fabre, P; Coudane, J; Higgs, P; Elineau, A; Pedrotti, M L; Gorsky, G; Ghiglione, J F
2018-05-01
Plastic pollution is widespread in ocean ecosystems worldwide, but it is unknown if plastic offers a unique habitat for bacteria compared to communities in the water column and attached to naturally-occurring organic particles. The large set of samples taken during the Tara-Mediterranean expedition revealed for the first time a clear niche partitioning between free-living (FL), organic particle-attached (PA) and the recently introduced plastic marine debris (PMD). Bacterial counts in PMD presented higher cell enrichment factors than generally observed for PA fraction, when compared to FL bacteria in the surrounding waters. Taxonomic diversity was also higher in the PMD communities, where higher evenness indicated a favorable environment for a very large number of species. Cyanobacteria were particularly overrepresented in PMD, together with essential functions for biofilm formation and maturation. The community distinction between the three habitats was consistent across the large-scale sampling in the Western Mediterranean basin. 'Plastic specific bacteria' recovered only on the PMD represented half of the OTUs, thus forming a distinct habitat that should be further considered for understanding microbial biodiversity in changing marine ecosystems. Copyright © 2017. Published by Elsevier Ltd.
Neural and cognitive plasticity: from maps to minds.
Mercado, Eduardo
2008-01-01
Some species and individuals are able to learn cognitive skills more flexibly than others. Learning experiences and cortical function are known to contribute to such differences, but the specific factors that determine an organism's intellectual capacities remain unclear. Here, an integrative framework is presented suggesting that variability in cognitive plasticity reflects neural constraints on the precision and extent of an organism's stimulus representations. Specifically, it is hypothesized that cognitive plasticity depends on the number and diversity of cortical modules that an organism has available as well as the brain's capacity to flexibly reconfigure and customize networks of these modules. The author relates this framework to past proposals on the neural mechanisms of intelligence, including (a) the relationship between brain size and intellectual capacity; (b) the role of prefrontal cortex in cognitive control and the maintenance of stimulus representations; and (c) the impact of neural plasticity and efficiency on the acquisition and performance of cognitive skills. The proposed framework provides a unified account of variability in cognitive plasticity as a function of species, age, and individual, and it makes specific predictions about how manipulations of cortical structure and function will impact intellectual capacity. Copyright (c) 2008 APA.
Karapanagioti, H K; Endo, S; Ogata, Y; Takada, H
2011-02-01
Plastic pellets found stranded on beaches are hydrophobic organic materials and thus, they are a favourable medium for persistent organic pollutants to absorb to. In the present study, plastic pellets are used to determine the diffuse pollution of selected Greek beaches. Samples of pellets were taken from these beaches and were analyzed for PCBs, DDTs, HCHs, and PAHs. The observed differences among pellets from various sampling sites are related to the pollution occurring at each site. Plastic pellets collected in Saronikos Gulf beaches demonstrate much higher pollutant loading than the ones collected in a remote island or close to an agricultural area. Based on data collected in this study and the International Pellet Watch program, pollution in Saronikos Gulf, Greece, is comparable to other heavily industrialized places of the world. The present study demonstrates the potential of pellet watch to be utilized as a detailed-scale monitoring tool within a single country. Copyright © 2010 Elsevier Ltd. All rights reserved.
Aluminum-based metal-air batteries
Friesen, Cody A.; Martinez, Jose Antonio Bautista
2016-01-12
Provided in one embodiment is an electrochemical cell, comprising: (i) a plurality of electrodes, comprising a fuel electrode that comprises aluminum and an air electrode that absorbs gaseous oxygen, the electrodes being operable in a discharge mode wherein the aluminum is oxidized at the fuel electrode and oxygen is reduced at the air electrode, and (ii) an ionically conductive medium, comprising an organic solvent; wherein during non-use of the cell, the organic solvent promotes formation of a protective interface between the aluminum of the fuel electrode and the ionically conductive medium, and wherein at an onset of the discharge mode, at least some of the protective interface is removed from the aluminum to thereafter permit oxidation of the aluminum during the discharge mode.
An ionic liquid-gated polymer thin film transistor with exceptionally low "on" resistance
NASA Astrophysics Data System (ADS)
Algarni, Saud A.; Althagafi, Talal M.; Smith, Patrick J.; Grell, Martin
2014-05-01
We report the ionic liquid (IL) gating of a solution processed semiconducting polymer, poly(2,5-bis(3-hexadecylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT). IL gating relies on the poor solubility of PBTTT, which requires hot chlorinated benzenes for solution processing. PBTTT, thus, resists dissolution even in IL, which otherwise rapidly dissolves semiconducting polymers. The resulting organic thin film transistors (OTFTs) display low threshold, very high carrier mobility (>3 cm2/Vs), and deliver high currents (in the order of 1 mA) at low operational voltages. Such OTFTs are interesting both practically, for the addressing of current-driven devices (e.g., organic LEDs), and for the study of charge transport in semiconducting polymers at very high carrier density.
Plastic Encapsulation of Stabilized Escherichia coli and Pseudomonas putida
Manzanera, M.; Vilchez, S.; Tunnacliffe, A.
2004-01-01
Escherichia coli and Pseudomonas putida dried in hydroxyectoine or trehalose are shown to be highly resistant to the organic solvents chloroform and acetone, and consequently, they can be encapsulated in a viable form in solid plastic materials. Bacteria are recovered by rehydration after physical disruption of the plastic. P. putida incorporated into a plastic coating of maize seeds was shown to colonize roots efficiently after germination. PMID:15128579
Lovinger, David M.; Kash, Thomas L.
2015-01-01
Long-lasting changes in synaptic function (i.e., synaptic plasticity) have long been thought to contribute to information storage in the nervous system. Although synaptic plasticity mainly has adaptive functions that allow the organism to function in complex environments, it is now clear that certain events or exposure to various substances can produce plasticity that has negative consequences for organisms. Exposure to drugs of abuse, in particular ethanol, is a life experience that can activate or alter synaptic plasticity, often resulting in increased drug seeking and taking and in many cases addiction. Two brain regions subject to alcohol’s effects on synaptic plasticity are the striatum and bed nucleus of the stria terminalis (BNST), both of which have key roles in alcohol’s actions and control of intake. The specific effects depend on both the brain region analyzed (e.g., specific subregions of the striatum and BNST) and the duration of ethanol exposure (i.e., acute vs. chronic). Plastic changes in synaptic transmission in these two brain regions following prolonged ethanol exposure are thought to contribute to excessive alcohol drinking and relapse to drinking. Understanding the mechanisms underlying this plasticity may lead to new therapies for treatment of these and other aspects of alcohol use disorder. PMID:26259092
SPECIATION OF ORGANICS IN WATER WITH RAMAN SPECTROSCOPY: UTILITY OF IONIC STRENGTH VARIATION
We have developed and are applying an experimental and mathematical method for describing the micro-speciation of complex organic contaminants in aqueous media. For our case, micro-speciation can be defined as qualitative and quantitative identification of all discrete forms of ...
Krašovec, Rok; Richards, Huw; Gifford, Danna R; Hatcher, Charlie; Faulkner, Katy J; Belavkin, Roman V; Channon, Alastair; Aston, Elizabeth; McBain, Andrew J; Knight, Christopher G
2017-08-01
Rates of random, spontaneous mutation can vary plastically, dependent upon the environment. Such plasticity affects evolutionary trajectories and may be adaptive. We recently identified an inverse plastic association between mutation rate and population density at 1 locus in 1 species of bacterium. It is unknown how widespread this association is, whether it varies among organisms, and what molecular mechanisms of mutagenesis or repair are required for this mutation-rate plasticity. Here, we address all 3 questions. We identify a strong negative association between mutation rate and population density across 70 years of published literature, comprising hundreds of mutation rates estimated using phenotypic markers of mutation (fluctuation tests) from all domains of life and viruses. We test this relationship experimentally, determining that there is indeed density-associated mutation-rate plasticity (DAMP) at multiple loci in both eukaryotes and bacteria, with up to 23-fold lower mutation rates at higher population densities. We find that the degree of plasticity varies, even among closely related organisms. Nonetheless, in each domain tested, DAMP requires proteins scavenging the mutagenic oxidised nucleotide 8-oxo-dGTP. This implies that phenotypic markers give a more precise view of mutation rate than previously believed: having accounted for other known factors affecting mutation rate, controlling for population density can reduce variation in mutation-rate estimates by 93%. Widespread DAMP, which we manipulate genetically in disparate organisms, also provides a novel trait to use in the fight against the evolution of antimicrobial resistance. Such a prevalent environmental association and conserved mechanism suggest that mutation has varied plastically with population density since the early origins of life.
Gifford, Danna R.; Hatcher, Charlie; Faulkner, Katy J.; Belavkin, Roman V.; Channon, Alastair; Aston, Elizabeth; McBain, Andrew J.
2017-01-01
Rates of random, spontaneous mutation can vary plastically, dependent upon the environment. Such plasticity affects evolutionary trajectories and may be adaptive. We recently identified an inverse plastic association between mutation rate and population density at 1 locus in 1 species of bacterium. It is unknown how widespread this association is, whether it varies among organisms, and what molecular mechanisms of mutagenesis or repair are required for this mutation-rate plasticity. Here, we address all 3 questions. We identify a strong negative association between mutation rate and population density across 70 years of published literature, comprising hundreds of mutation rates estimated using phenotypic markers of mutation (fluctuation tests) from all domains of life and viruses. We test this relationship experimentally, determining that there is indeed density-associated mutation-rate plasticity (DAMP) at multiple loci in both eukaryotes and bacteria, with up to 23-fold lower mutation rates at higher population densities. We find that the degree of plasticity varies, even among closely related organisms. Nonetheless, in each domain tested, DAMP requires proteins scavenging the mutagenic oxidised nucleotide 8-oxo-dGTP. This implies that phenotypic markers give a more precise view of mutation rate than previously believed: having accounted for other known factors affecting mutation rate, controlling for population density can reduce variation in mutation-rate estimates by 93%. Widespread DAMP, which we manipulate genetically in disparate organisms, also provides a novel trait to use in the fight against the evolution of antimicrobial resistance. Such a prevalent environmental association and conserved mechanism suggest that mutation has varied plastically with population density since the early origins of life. PMID:28837573
Rochman, Chelsea M; Hoh, Eunha; Hentschel, Brian T; Kaye, Shawn
2013-02-05
Concerns regarding marine plastic pollution and its affinity for chemical pollutants led us to quantify relationships between different types of mass-produced plastic and organic contaminants in an urban bay. At five locations in San Diego Bay, CA, we measured sorption of polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) throughout a 12-month period to the five most common types of mass-produced plastic: polyethylene terephthalate (PET), high-density polyethylene (HDPE), polyvinyl chloride (PVC), low-density polyethylene (LDPE), and polypropylene (PP). During this long-term field experiment, sorption rates and concentrations of PCBs and PAHs varied significantly among plastic types and among locations. Our data suggest that for PAHs and PCBs, PET and PVC reach equilibrium in the marine environment much faster than HDPE, LDPE, and PP. Most importantly, concentrations of PAHs and PCBs sorbed to HDPE, LDPE, and PP were consistently much greater than concentrations sorbed to PET and PVC. These data imply that products made from HDPE, LDPE, and PP pose a greater risk than products made from PET and PVC of concentrating these hazardous chemicals onto fragmented plastic debris ingested by marine animals.
NASA Astrophysics Data System (ADS)
Kaufman, Don; Wright, Geoff; Kroemer, Ryan; Engel, Josh
1999-11-01
This paper describes work done to develop a meaningful undergraduate organic lab activity that illustrates chemistry of the real world while utilizing reactions typically included in the organic lecture and lab. We show how a common plastic can be converted into several compounds using ester hydrolysis and SN2 reactions. Contributing to the critical shortage of landfill space faced by many communities is the large quantity of plastic refuse. Thus, there is a real need to recycle plastic products. One way to recycle plastics such as polyethyleneterephthalate (PET), the polyester from which numerous consumer products such as 2-liter soda bottles are made, is to depolymerize them and then to use the resulting monomers to produce new products. PET is industrially depolymerized via an acid-catalyzed transesterification reaction conducted under conditions of high temperature and pressure that are not feasible in the undergraduate lab. Despite literature reports that PET is remarkably resistant to hydrolysis, we found that PET can be readily hydrolyzed by refluxing with potassium hydroxide or potassium tert-butoxide in amyl alcohol to give terephthalic acid in high yield. It is then possible to readily synthesize terephthalate diesters via SN2 reactions of ammonium terephthalate salts with alkyl halides. Fischer esterification can also be used to prepare the diesters, but yields are significantly lower.
Study of Selected Composites Copper Concentrate-Plastic Waste Using Thermal Analysis
NASA Astrophysics Data System (ADS)
Szyszka, Danuta
2017-12-01
The paper presents thermal analysis of selected composites (copper concentrate, plastic waste) in two stages. The first stage consisted in thermogravimetric analysis and differential thermal analysis on the applied plastic waste and copper concentrate, and subsequently, a comparative study has been carried out on products obtained, constituting composites of those materials. As a result of analyses, it was found that up to ca. 400 °C composites show high thermal stability, whereas above that temperature, a thermal decomposition of the composite occurs, resulting in emissions of organic compounds, i.e. hydrocarbon compounds and organic oxygenate derivatives.
NASA Astrophysics Data System (ADS)
Gohel, Khushbu; Kanchan, D. K.
Poly(vinylidene fluoride-hexafluropropylene) (PVDF-HFP) and poly(methyl methacrylate) (PMMA)-based gel polymer electrolytes (GPEs) comprising propylene carbonate and diethyl carbonate mixed plasticizer with variation of lithium perchlorate (LiClO4) salt concentrations have been prepared using a solvent casting technique. Structural characterization has been carried out using XRD wherein diffraction pattern reveals the amorphous nature of sample up to 7.5wt.% salt and complexation of polymers and salt have been studied by FTIR analysis. Surface morphology of the samples has been studied using scanning electron microscope. Electrochemical impedance spectroscopy in the temperature range 303-363K has been carried out for electrical conductivity. The maximum room temperature conductivity of 2.83×10-4S cm-1 has been observed for the GPE incorporating 7.5wt.% LiClO4. The temperature dependence of ionic conductivity obeys the Arrhenius relation. The increase in ionic conductivity with change in temperatures and salt content is observed. Transport number measurement is carried out by Wagner’s DC polarization method. Loss tangent (tan δ) and imaginary part of modulus (M‧‧) corresponding to dielectric relaxation and conductivity relaxation respectively show faster relaxation process with increasing salt content up to optimum value of 7.5wt.% LiClO4. The modulus (M‧‧) shows that the conductivity relaxation is of non-Debye type (broader than Debye peak).
Soft and flexible PEDOT/PSS films for applications to soft actuators
NASA Astrophysics Data System (ADS)
Li, Yuechen; Tanigawa, Ryo; Okuzaki, Hidenori
2014-07-01
Stretchable and highly conductive PEDOT/PSS/Xyl films were prepared by casting an aqueous dispersion of poly(3,4-ethylenedioxythiophene) doped with poly(4-styrenesulfonate) (PEDOT/PSS) as colloidal gel particles containing xylitol (Xyl) and subsequent heating. The electrical conductivity of the PEDOT/PSS/Xyl film containing 50 wt% of xylitol significantly increased from 115 S cm-1 to 407 S cm-1 by heating at 140 °C in air for 1 h. It was found that the xylitol had two functions as (i) a plasticizer to weaken hydrogen bonds between PSS of colloidal particles by replacing with that between xylitol and PSS and (ii) the additional capability of increasing the mobility of charge carriers between the colloidal particles. The transparent ionic liquid/polyurethane (IL/PU) gels were fabricated by dissolving thermoplastic polyurethane and ionic liquid of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. By increasing the IL content from 0 wt% to 70 wt%, both ionic conductivity and electric-double-layer capacitance under an electric field increased, while Young’s modulus, strength and elongation at break decreased. The IL/PU/PEDOT/PSS/Xyl composites were fabricated by sandwiching the IL/PU gel between two soft and flexible PEDOT/PSS/Xyl films. Upon application of 2 V, the IL/PU/PEDOT/PSS/Xyl composite (IL = 70%) showed quick and intensive bending toward anode, where the bending displacement at 0.1 Hz attained 2.9 mm, corresponding to the strain of 0.15%, and still worked at frequencies higher than 50 Hz.
Kim, Wonbin; Kim, Woong
2016-06-03
Stretchable supercapacitors often have laminated structures consisting of electrode, electrolyte, and supporting layers. Since the layers are likely to be composed of different materials, delamination is a major cause of failure upon stretching. In this study, we demonstrate delamination-free stretchable supercapacitors where all the component layers are prepared with a single matrix, which is composed of a polymer, poly(vinylidene fluoride-hexafluoropropylene) and an ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. Since the ionic liquid in the composite plays a role as both an electrolyte and a plasticizer, this composite can be used as an electrolyte and a supporting layer in the stretchable supercapacitor. The electrode layer can be fabricated by incorporating carbon nanotubes in the common matrix. Then, all the layers can be seamlessly fused into one body by dissolving the surface of the composite with acetone, which evaporates after the integration, leaving no borders between the layers. This one-body stretchable supercapacitor not only has high durability against repetitive stretches but also is stretchable in all directions. This feature clearly distinguishes them from conventional stretchable supercapacitors fabricated using buckled structures, which are stretchable only in one or two directions. Moreover, this supercapacitor has high cell voltage (∼3 V) owing to the ionic liquid-based gel electrolytes. Our demonstration of isotropically stretchable high-durability supercapacitors may have a great implication in the development of stretchable energy storage devices for real applications.
Canopy Dynamics in Nanoscale Ionic Materials Probed by NMR
NASA Astrophysics Data System (ADS)
Mirau, Peter
2013-03-01
Nanoscale ionic materials (NIMs) are hybrids prepared from ionically functionalized nanoparticles (NP) neutralized by oligomeric polymer counter-ions. NIMs are designed to behave as liquids under ambient conditions in the absence of solvent and have no volatile organic content, making them useful for a number of applications. We have used NMR relaxation and pulse-field gradient NMR to probe local and collective canopy dynamics in NIMs based on silica nanoparticles (NP), fullerols and proteins in order to understand the relationship between the core and canopy structure and the bulk properties. The NMR studies show that the canopy dynamics depend on the degree of neutralization, the canopy radius of gyration and molecular crowding at the ionically modified NP surface. The viscosity in NIMs can be directly controlled with the addition of ions that enhance the exchange rate for polymers at the NP surface. These results show that NIMs for many applications can be prepared by controlling the dynamics of the NP interface.
Surface-bonded ionic liquid stationary phases in high-performance liquid chromatography--a review.
Pino, Verónica; Afonso, Ana M
2012-02-10
Ionic liquids (ILs) are a class of ionic, nonmolecular solvents which remain in liquid state at temperatures below 100°C. ILs possess a variety of properties including low to negligible vapor pressure, high thermal stability, miscibility with water or a variety of organic solvents, and variable viscosity. IL-modified silica as novel high-performance liquid chromatography (HPLC) stationary phases have attracted considerable attention for their differential behavior and low free-silanol activity. Indeed, around 21 surface-confined ionic liquids (SCIL) stationary phases have been developed in the last six years. Their chromatographic behavior has been studied, and, despite the presence of a positive charge on the stationary phase, they showed considerable promise for the separation of neutral solutes (not only basic analytes), when operated in reversed phase mode. This aspect points to the potential for truly multimodal stationary phases. This review attempts to summarize the state-of-the-art about SCIL phases including their preparation, chromatographic behavior, and analytical performance. Copyright © 2011 Elsevier B.V. All rights reserved.
Electrochemistry of sulfur and polysulfides in ionic liquids.
Manan, Ninie S A; Aldous, Leigh; Alias, Yatimah; Murray, Paul; Yellowlees, Lesley J; Lagunas, M Cristina; Hardacre, Christopher
2011-12-01
The electrochemistry of elemental sulfur (S(8)) and the polysulfides Na(2)S(4) and Na(2)S(6) has been studied for the first time in nonchloroaluminate ionic liquids. The cyclic voltammetry of S(8) in the ionic liquids is different to the behavior reported in some organic solvents, with two reductions and one oxidation peak observed. Supported by in situ UV-vis spectro-electrochemical experiments, the main reduction products of S(8) in [C(4)mim][DCA] ([C(4)mim] = 1-butyl-3-methylimidazolium; DCA = dicyanamide) have been identified as S(6)(2-) and S(4)(2-), and plausible pathways for the formation of these species are proposed. Dissociation and/or disproportionation of the polyanions S(6)(2-) and S(4)(2-) appears to be slow in the ionic liquid, with only small amounts of the blue radical species S(3)(•-) formed in the solutions at r.t., in contrast with that observed in most molecular solvents. © 2011 American Chemical Society
The solvation structures of cellulose microfibrils in ionic liquids.
Mostofian, Barmak; Smith, Jeremy C; Cheng, Xiaolin
2011-12-01
The use of ionic liquids for non-derivatized cellulose dissolution promises an alternative method for the thermochemical pretreatment of biomass that may be more efficient and environmentally acceptable than more conventional techniques in aqueous solution. Here, we performed equilibrium MD simulations of a cellulose microfibril in the ionic liquid 1-butyl-3-methylimidazolium chloride (BmimCl) and compared the solute structure and the solute-solvent interactions at the interface with those from corresponding simulations in water. The results indicate a higher occurrence of solvent-exposed orientations of cellulose surface hydroxymethyl groups in BmimCl than in water. Moreover, spatial and radial distribution functions indicate that hydrophilic surfaces are a preferred site of interaction between cellulose and the ionic liquid. In particular, hydroxymethyl groups on the hydrophilic fiber surface adopt a different conformation from their counterparts oriented towards the fiber's core. Furthermore, the glucose units with these solvent-oriented hydroxymethyls are surrounded by the heterocyclic organic cation in a preferred parallel orientation, suggesting a direct and distinct interaction scheme between cellulose and BmimCl.
Pang, Long; Yang, Peijie; Pang, Rong; Li, Shunyi
2017-08-01
1-Hexadecyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide is a solid-phase ionic organic material under ambient temperature and is considered as a kind of "frozen" ionic liquid. Because of their solid-state and ultra-hydrophobicity, "frozen" ionic liquids are able to be confined in the pores of hollow fiber, based on which a simple method was developed for the hollow-fiber solid-phase microextraction of dichlorodiphenyltrichloroethane and its main metabolites. Under optimized conditions, the proposed method results in good linearity (R 2 > 0.9965) over the range of 0.5-50 μg/L, with low limits of detection and quantification in the range of 0.33-0.38 and 1.00-1.25 μg/L, respectively. Intra- and interday precisions evaluated by relative standard deviation were 3-6 and 1-6%, respectively. The spiked recoveries of dichlorodiphenyltrichloroethane and its main metabolites from real water samples were in the range of 64-113 and 79-112%, respectively, at two different concentration levels. The results suggest that "frozen" ionic liquids are promising for use as a class of novel sorbents. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Padró, Juan M; Pellegrino Vidal, Rocío B; Reta, Mario
2014-12-01
The partition coefficients, P IL/w, of several compounds, some of them of biological and pharmacological interest, between water and room-temperature ionic liquids based on the imidazolium, pyridinium, and phosphonium cations, namely 1-octyl-3-methylimidazolium hexafluorophosphate, N-octylpyridinium tetrafluorophosphate, trihexyl(tetradecyl)phosphonium chloride, trihexyl(tetradecyl)phosphonium bromide, trihexyl(tetradecyl)phosphonium bis(trifluoromethylsulfonyl)imide, and trihexyl(tetradecyl)phosphonium dicyanamide, were accurately measured. In this way, we extended our database of partition coefficients in room-temperature ionic liquids previously reported. We employed the solvation parameter model with different probe molecules (the training set) to elucidate the chemical interactions involved in the partition process and discussed the most relevant differences among the three types of ionic liquids. The multiparametric equations obtained with the aforementioned model were used to predict the partition coefficients for compounds (the test set) not present in the training set, most being of biological and pharmacological interest. An excellent agreement between calculated and experimental log P IL/w values was obtained. Thus, the obtained equations can be used to predict, a priori, the extraction efficiency for any compound using these ionic liquids as extraction solvents in liquid-liquid extractions.
Ionic Liquids and Poly(ionic liquid)s for Morphosynthesis of Inorganic Materials.
Gao, Min-Rui; Yuan, Jiayin; Antonietti, Markus
2017-04-24
Ionic liquids (ILs) are new, innovative ionic solvents with rich physicochemical properties and intriguing pre-organized solvent structures; these materials offer great potential to impact across versatile areas of scientific research, for example, synthetic inorganic chemistry. Recent use of ILs as precursors, templates, and solvents has led to inorganic materials with tailored sizes, dimensionalities, morphologies, and functionalities that are difficult to obtain, or even not accessible, by using conventional solvents. Poly(ionic liquid)s (PILs) polymerized from IL monomers also raise the prospect of modifying nucleation, growth, and crystallization of inorganic objects, shedding light on the synthesis of a wide range of new materials. Here we survey recent key progress in using ILs and PILs in the field of synthetic inorganic chemistry. As well as highlighting the unique features of ILs and PILs that enable advanced synthesis, the effects of adding other solvents to the final products, along with the emerging applications of the created inorganic materials will be discussed. We finally provide an outlook on several development opportunities that could lead to new advancements of this exciting research field. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Lin, Xinrong; Chapman Varela, Jennifer; Grinstaff, Mark W
2016-12-20
The chemical instability of the traditional electrolyte remains a safety issue in widely used energy storage devices such as Li-ion batteries. Li-ion batteries for use in devices operating at elevated temperatures require thermally stable and non-flammable electrolytes. Ionic liquids (ILs), which are non-flammable, non-volatile, thermally stable molten salts, are an ideal replacement for flammable and low boiling point organic solvent electrolytes currently used today. We herein describe the procedures to: 1) synthesize mono- and di-phosphonium ionic liquids paired with chloride or bis(trifluoromethane)sulfonimide (TFSI) anions; 2) measure the thermal properties and stability of these ionic liquids by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA); 3) measure the electrochemical properties of the ionic liquids by cyclic voltammetry (CV); 4) prepare electrolytes containing lithium bis(trifluoromethane)sulfonamide; 5) measure the conductivity of the electrolytes as a function of temperature; 6) assemble a coin cell battery with two of the electrolytes along with a Li metal anode and LiCoO2 cathode; and 7) evaluate battery performance at 100 °C. We additionally describe the challenges in execution as well as the insights gained from performing these experiments.
L.R. Seifert-Monson; B.H. Hill; R.K. Kolka; T.M. Jicha; L.L. Lehto; C.M. Elonen
2014-01-01
Export of dissolved organic carbon from lakes and streams has increased throughout Europe and North America over the past several decades. One possible cause is altered deposition chemistry; specifically, decreasing sulfate inputs leading to changes in ionic strength and dissolved organic carbon solubility. To further investigate the relationship between deposition...
Fuentes, Manuel; Pessela, Benevides C C; Maquiese, Jorgette V; Ortiz, Claudia; Segura, Rosa L; Palomo, Jose M; Abian, Olga; Torres, Rodrigo; Mateo, Cesar; Fernández-Lafuente, Roberto; Guisán, J M
2004-01-01
New and strong ionic exchange resins have been prepared by the simple and rapid ionic adsorption of anionic polymers (sulfate-dextran) on porous supports activated with the opposite ionic group (DEAE/MANAE). Ionic exchange properties of such composites were strongly dependent on the size of the ionic polymers as well as on the conditions of the ionic coating of the solids with the ionic polymers (optimal conditions were 400 mg of sulfate-dextran 5000 kDa per gram of support). Around 80% of the proteins contained in crude extracts from Escherichia coli and Acetobacter turbidans could be adsorbed on these porous composites even at pH 7. This interaction was stronger than that using conventional carboxymethyl cellulose (CMC) and even others such as supports coated with aspartic-dextran polymer. By means of the sequential use of the new supports and supports coated with polyethyleneimine (PEI), all proteins from crude extracts could be immobilized. In fact, a large percentage (over 50%) could be immobilized on both supports. Finally, some industrially relevant enzymes (beta-galactosidases from Aspergillus oryzae, Kluyveromyces lactis, and Thermussp. strain T2, lipases from Candida antarctica A and B, Candida rugosa, Rhizomucor miehei, and Rhyzopus oryzae and bovine pancreas trypsin and chymotrypsin) have been immobilized on these supports with very high activity recoveries and immobilization rates. After enzyme inactivation, the protein could be fully desorbed from the support, and then the support could be reused for several cycles. Moreover, in some instances the enzyme stability was significantly improved, mainly in the presence of organic solvents, perhaps as a consequence of the highly hydrophilic microenvironment of the support.
Paluch, Marian; Wojnarowska, Zaneta; Goodrich, Peter; Jacquemin, Johan; Pionteck, Jürgen; Hensel-Bielowka, Stella
2015-08-28
Electrical conductivity of the supercooled ionic liquid [C8MIM][NTf2], determined as a function of temperature and pressure, highlights strong differences in its ionic transport behavior between low and high temperature regions. To date, the crossover effect which is very well known for low molecular van der Waals liquids has been rarely described for classical ionic liquids. This finding highlights that the thermal fluctuations could be dominant mechanisms driving the dramatic slowing down of ion motions near Tg. An alternative way to analyze separately low and high temperature dc-conductivity data using a density scaling approach was then proposed. Based on which a common value of the scaling exponent γ = 2.4 was obtained, indicating that the applied density scaling is insensitive to the crossover effect. By comparing the scaling exponent γ reported herein along with literature data for other ionic liquids, it appears that γ decreases by increasing the alkyl chain length on the 1-alkyl-3-methylimidazolium-based ionic liquids. This observation may be related to changes in the interaction between ions in solution driven by an increase in the van der Waals type interaction by increasing the alkyl chain length on the cation. This effect may be related to changes in the ionic liquid nanostructural organization with the alkyl chain length on the cation as previously reported in the literature based on molecular dynamic simulations. In other words, the calculated scaling exponent γ may be then used as a key parameter to probe the interaction and/or self-organizational changes in solution with respect to the ionic liquid structure.
Lithner, Delilah; Nordensvan, Ildikó; Dave, Göran
2012-06-01
The large global production of plastics and their presence everywhere in the society and the environment create a need for assessing chemical hazards and risks associated with plastic products. The aims of this study were to determine and compare the toxicity of leachates from plastic products made of five plastics types and to identify the class of compounds that is causing the toxicity. Selected plastic types were those with the largest global annual production, that is, polypropylene, polyethylene, and polyvinyl chloride (PVC), or those composed of hazardous monomers (e.g., PVC, acrylonitrile-butadiene-styrene [ABS], and epoxy). Altogether 26 plastic products were leached in deionized water (3 days at 50°C), and the water phases were tested for acute toxicity to Daphnia magna. Initial Toxicity Identification Evaluations (C18 filtration and EDTA addition) were performed on six leachates. For eleven leachates (42%) 48-h EC50s (i.e the concentration that causes effect in 50 percent of the test organisms) were below the highest test concentration, 250 g plastic/L. All leachates from plasticized PVC (5/5) and epoxy (5/5) products were toxic (48-h EC50s ranging from 2 to 235 g plastic/L). None of the leachates from polypropylene (5/5), ABS (5/5), and rigid PVC (1/1) products showed toxicity, but one of the five tested HDPE leachates was toxic (48-h EC50 17-24 g plastic/L). Toxicity Identification Evaluations indicated that mainly hydrophobic organics were causing the toxicity and that metals were the main cause for one leachate (metal release was also confirmed by chemical analysis). Toxic chemicals leached even during the short-term leaching in water, mainly from plasticized PVC and epoxy products.
Yang, Xiaoning; Sun, Lushi; Xiang, Jun; Hu, Song; Su, Sheng
2013-02-01
Plastics from waste electrical and electronic equipment (WEEE) have been an important environmental problem because these plastics commonly contain toxic halogenated flame retardants which may cause serious environmental pollution, especially the formation of carcinogenic substances polybrominated dibenzo dioxins/furans (PBDD/Fs), during treat process of these plastics. Pyrolysis has been proposed as a viable processing route for recycling the organic compounds in WEEE plastics into fuels and chemical feedstock. However, dehalogenation procedures are also necessary during treat process, because the oils collected in single pyrolysis process may contain numerous halogenated organic compounds, which would detrimentally impact the reuse of these pyrolysis oils. Currently, dehalogenation has become a significant topic in recycling of WEEE plastics by pyrolysis. In order to fulfill the better resource utilization of the WEEE plastics, the compositions, characteristics and dehalogenation methods during the pyrolysis recycling process of WEEE plastics were reviewed in this paper. Dehalogenation and the decomposition or pyrolysis of WEEE plastics can be carried out simultaneously or successively. It could be 'dehalogenating prior to pyrolysing plastics', 'performing dehalogenation and pyrolysis at the same time' or 'pyrolysing plastics first then upgrading pyrolysis oils'. The first strategy essentially is the two-stage pyrolysis with the release of halogen hydrides at low pyrolysis temperature region which is separate from the decomposition of polymer matrixes, thus obtaining halogenated free oil products. The second strategy is the most common method. Zeolite or other type of catalyst can be used in the pyrolysis process for removing organohalogens. The third strategy separate pyrolysis and dehalogenation of WEEE plastics, which can, to some degree, avoid the problem of oil value decline due to the use of catalyst, but obviously, this strategy may increase the cost of whole recycling process. Copyright © 2012 Elsevier Ltd. All rights reserved.
Export of dissolved organic carbon from lakes and streams has increased throughout Europe and North America over the past several decades. One possible cause is altered deposition chemistry; specifically, decreasing sulfate inputs leading to changes in ionic strength and dissolve...
NASA Astrophysics Data System (ADS)
Barra, M.; Viggiano, D.; Di Capua, R.; Di Girolamo, F.; Santoro, F.; Taglialatela, M.; Cassinese, A.
2012-02-01
The possibility of the fabrication of organic devices suitable to be applied in bio-sensing fields depends largely on the availability of organic compounds displaying robust electrical properties even in aqueous solutions and effective biocompatibility features. In this paper, we report about the good cellular biocompatibility and the electrical response stability in an ionic medium of n-type organic transistors based on the recently developed PDI-8CN2 oligomer. The biocompatibility has been tested by analyzing the adhesion and viability of two different cell lines, human epithelial HeLa cells and murine neuronal F11 cells, on PDI-8CN2 films grown by organic molecular beam deposition (OMBD) on SiO2 substrates. The effect of film thickness on cell attachment was also tested. Uncoated SiO2 substrates were used as control surfaces and sexithiophene (T6) as device testing control. Moreover, the possible toxicity of -CN groups of PDI-8CN2 was tested on HeLa cell cultures, using PDI-8 and T6 molecules as controls. Results showed that, although at high concentration these organic compounds are toxic in solution, if they are presented in form of film, cell lines can attach and grow on them. The electrical response stability of PDI-8CN2 transistors in a cellular culture medium characterized by high concentrations of ionic species has been also investigated. For this purpose, low-voltage operation devices with VGS ranging from -5 V to 5 V, able to strongly reduce the influence of Faradaic currents coming from the electrical operation in an highly ionic environment, have been fabricated on 35 nm thick SiO2 layers and electrically characterized. These results are useful to experimentally define the main critical issues to be further addressed for the fabrication of reliable bio-sensors based on organic transistors.
Wang, Mingkui; Anghel, Alina M; Marsan, Benoît; Cevey Ha, Ngoc-Le; Pootrakulchote, Nuttapol; Zakeeruddin, Shaik M; Grätzel, Michael
2009-11-11
We report an efficient nonplatinized flexible counter electrode for dye-sensitized solar cells. In combination with a solvent-free ionic liquid electrolyte, we have demonstrated a approximately 6.5% cell with an amphiphilic ruthenium polypyridyl photosensitizer showing excellent stability measured under prolonged light soaking at 60 degrees C. Compared to the Pt deposited PEN film, the CoS deposited PEN film shows higher electrocatalytic activity for the reduction of triiodide. This is expected to have an important practical consequence on the production of flexible low-cost and lightweight thin film DSC devices based on the plastic matrix.
Pastor, María Jesús; Cuerva, Cristián; Campo, José A; Schmidt, Rainer; Torres, María Rosario; Cano, Mercedes
2016-05-12
Ionic liquid crystals (ILCs) allow the combination of the high ionic conductivity of ionic liquids (ILs) with the supramolecular organization of liquid crystals (LCs). ILCs salts were obtained by the assembly of long-chained diketonylpyridinium cations of the type [HOO R(n)pyH ]⁺ and BF₄ - , ReO₄ - , NO₃ - , CF₃SO₃ - , CuCl₄ 2- counter-ions. We have studied the thermal behavior of five series of compounds by differential scanning calorimetry (DSC) and hot stage polarized light optical microscopy (POM). All materials show thermotropic mesomorphism as well as crystalline polymorphism. X-ray diffraction of the [HOO R(12)pyH ][ReO₄] crystal reveals a layered structure with alternating polar and apolar sublayers. The mesophases also exhibit a lamellar arrangement detected by variable temperature powder X-ray diffraction. The CuCl₄ 2- salts exhibit the best LC properties followed by the ReO₄ - ones due to low melting temperature and wide range of existence. The conductivity was probed for the mesophases in one species each from the ReO₄ - , and CuCl₄ 2- families, and for the solid phase in one of the non-mesomorphic Cl - salts. The highest ionic conductivity was found for the smectic mesophase of the ReO₄ - containing salt, whereas the solid phases of all salts were dominated by electronic contributions. The ionic conductivity may be favored by the mesophase lamellar structure.
NMR Study of Ion Dynamics and Charge Storage in Ionic Liquid Supercapacitors
2015-01-01
Ionic liquids are emerging as promising new electrolytes for supercapacitors. While their higher operating voltages allow the storage of more energy than organic electrolytes, they cannot currently compete in terms of power performance. More fundamental studies of the mechanism and dynamics of charge storage are required to facilitate the development and application of these materials. Here we demonstrate the application of nuclear magnetic resonance spectroscopy to study the structure and dynamics of ionic liquids confined in porous carbon electrodes. The measurements reveal that ionic liquids spontaneously wet the carbon micropores in the absence of any applied potential and that on application of a potential supercapacitor charging takes place by adsorption of counterions and desorption of co-ions from the pores. We find that adsorption and desorption of anions surprisingly plays a more dominant role than that of the cations. Having elucidated the charging mechanism, we go on to study the factors that affect the rate of ionic diffusion in the carbon micropores in an effort to understand supercapacitor charging dynamics. We show that the line shape of the resonance arising from adsorbed ions is a sensitive probe of their effective diffusion rate, which is found to depend on the ionic liquid studied, as well as the presence of any solvent additives. Taken as whole, our NMR measurements allow us to rationalize the power performances of different electrolytes in supercapacitors. PMID:25973552
Prominent roles of impurities in ionic liquid for catalytic conversion of carbohydrates
DOE Office of Scientific and Technical Information (OSTI.GOV)
Zhao, Haibo; Brown, Heather M.; Holladay, Johnathan E.
2012-02-07
In the last two decades, ionic liquids have emerged as new and versatile solvents, and many of them are also catalysts for a broad range of catalytic reactions. Certain ionic liquids have been found to possess the unique capability of dissolving cellulosic biomass. The potential of such ionic liquids as solvent to enable catalytic conversion of cellulosic polymers was first explored and demonstrated by Zhao et al. This field of research has since experienced a rapid growth. Most ionic liquids have negligible vapor pressure and excellent thermal stability over a wide temperature range. For example, ionic liquids composed of 1-ethyl-3-methylimidazoliummore » (EMIM+) cation and Cl- anion was reported to be stable up to 285 C, while salts of the same cation with other anions such as BF4- and PF6- are thermally stable above 380 C under inert atmosphere. It is well known that presence of impurities in ionic liquids typically causes changes in physical properties, e.g. decreasing in melting point and viscosity. Addition of Lewis acidic metal chlorides, e.g. AlCl3 to 1-alkyl-3-methylimidazolium chloride, [AMIM]Cl, is an exothermic reaction and considerably reduces the melting point by forming [AMIM]AlCl4 or [AMIM]Al2Cl7 that are also ionic liquids but have much lower melting point than the parent [AMIM]Cl. While most early research on catalysis of ionic liquids involving metallohalide anions were typically conducted from stoichiometric ratio of such anions to organic cations, e.g. [AMIM]+, the use of pure ionic liquids only as a solvent to carry out catalysis by a catalytic amount of a metal halide as catalyst truly displayed the solvent property of such ionic liquids.4 In such reaction systems, catalytic amounts of metal halides were used to catalyze the conversion of glucose and cellulose.4,11,12 The metal chloride catalyst concentration was in the order of 10-3 M. The presence of another metal chloride in the ionic liquids, even in the order of 10-5 M concentration was found to bring a dramatic synergistic effect. Therefore, the catalytic performance of the metal halide catalyst for the conversion of carbohydrates in the ionic liquid systems is highly sensitive to the presence of impurities. This work presents findings on the role of impurities that were present in some commercially available ionic liquids used for the conversion of the cellulose.« less
Janes, Lindsay; Lanier, Steven T; Evans, Gregory R D; Kasten, Steven J; Hume, Keith M; Gosain, Arun K
2017-08-01
Although recent estimates predict a large impending shortage of plastic surgeons, graduate medical education funding through the Centers for Medicare and Medicaid Services remains capped by the 1997 Balanced Budget Act. The authors' aim was to develop a plan to stimulate legislative action. The authors reviewed responses of the American Society of Plastic Surgeons, American College of Surgeons, and American Medical Association from January of 2015 to a House Energy & Commerce Committee request for input on graduate medical education funding. In addition, all program directors in plastic surgery were surveyed through the American Council of Academic Plastic Surgeons to determine their graduate medical education funding sources. All three organizations agree that current graduate medical education funding is inadequate to meet workforce needs, and this has a significant impact on specialty selection and distribution for residency training. All agreed that funding should be tied to the resident rather than to the institution, but disagreed on whether funds should be divided between direct (allocated to residency training) and indirect (allocated to patient care) pools, as is currently practiced. Program directors' survey responses indicated that only 38 percent of graduate medical education funds comes from the Centers for Medicare and Medicaid Services. Organized medicine is at risk of losing critically needed graduate medical education funding. Specific legislation to support additional graduate medical education positions and funding (House Resolutions 1180 and 4282) has been proposed but has not been universally endorsed, in part because of a lack of collaboration in organized medicine. Collaboration among major organizations can reinvigorate these measures and implement real change in funding.
Formiga, A T; Silveira, F A O; Fernandes, G W; Isaias, R M S
2015-03-01
Understanding factors that modulate plant development is still a challenging task in plant biology. Although research has highlighted the role of abiotic and biotic factors in determining final plant structure, we know little of how these factors combine to produce specific developmental patterns. Here, we studied patterns of cell and tissue organisation in galled and non-galled organs of Baccharis reticularia, a Neotropical shrub that hosts over ten species of galling insects. We employed qualitative and quantitative approaches to understand patterns of growth and differentiation in its four most abundant gall morphotypes. We compared two leaf galls induced by sap-sucking Hemiptera and stem galls induced by a Lepidopteran and a Dipteran, Cecidomyiidae. The hypotheses tested were: (i) the more complex the galls, the more distinct they are from their non-galled host; (ii) galls induced on less plastic host organs, e.g. stems, develop under more morphogenetic constraints and, therefore, should be more similar among themselves than galls induced on more plastic organs. We also evaluated the plant sex preference of gall-inducing insects for oviposition. Simple galls were qualitative and quantitatively more similar to non-galled organs than complex galls, thereby supporting the first hypothesis. Unexpectedly, stem galls had more similarities between them than to their host organ, hence only partially supporting the second hypothesis. Similarity among stem galls may be caused by the restrictive pattern of host stems. The opposite trend was observed for host leaves, which generate either similar or distinct gall morphotypes due to their higher phenotypic plasticity. The Relative Distance of Plasticity Index for non-galled stems and stem galls ranged from 0.02 to 0.42. Our results strongly suggest that both tissue plasticity and gall inducer identity interact to determine plant developmental patterns, and therefore, final gall structure. © 2014 German Botanical Society and The Royal Botanical Society of the Netherlands.
Plastics in the marine environment: the dark side of a modern gift.
Hammer, Jort; Kraak, Michiel H S; Parsons, John R
2012-01-01
Plastics are cheap, strong, and durable and offer considerable benefits to humanity. They potentially can enhance the benefits that both medical and scientific technology will bestow to humankind. However, it has now been several decades since the use of plastics exploded, and we have evidence that our current approach to production, use, transport and disposal of plastic materials has caused, and is still causing serious effects on wildlife, and is not sustainable. Because of frequent inappropriate waste management practices, or irresponsible human behavior, large masses of plastic items have been released into the environment, and thereby have entered the world's oceans. Moreover, this process continues, and in some places is even increasing. Most plastic debris that now exists in the marine environment originated from ocean-based sources such as the fishing industry. Plastics accumulate in coastal areas, at the ocean surface and on the seabed. Because 70% of all plastics are known to eventually sink, it is suspected that ever increasing amounts of plastic items are accumulating in seabed sediments. Plastics do not biodegrade, although, under the influence of solar UV radiations, plastics do degrade and fragment into small particles, termed microplastics. Our oceans eventually serve as a sink for these small plastic particles and in one estimate, it is thought that 200,000 microplastics per km(2) of the ocean's surface commonly exist. The impact of plastic debris has been studied since the beginning of the 1960's. To date, more than 267 species in the marine environment are known to have been affected by plastic entanglement or ingestion. Marine mammals are among those species that are most affected by entanglement in plastic debris. By contrast, marine birds suffer the most from ingestion of plastics. Organisms can also be seriously absorbed by floating plastic debris, or the contaminants may derive from plastic additives that are leached to the environment. Recent studies emphasize the important role of microplastics as they are easily ingestible by small organisms, such as plankton species, and form a pathway for contaminants to enter the food web. Contaminants leached from plastics tend to bioaccumulate in those organisms that absorb them, and chemical concentrations are often higher at higher trophic levels. This causes a threat to the basis of every food web and can have serious and far-reaching effects, even on nonmarine species such as polar bears and humans, who consume marine-grown food. Therefore, resolving the plastic debris problem is important to human kind for two reasons: we are both creator, and victim of the plastic pollution problem. Solutions to the plastic debris problem can only be achieved through a combination of actions. Such actions include the following: Legislation against marine pollution by plastics must be enforced, recycling must be accentuated, alternatives (biodegradable) to current plastic products must be found, and clean-up of debris must proceed, if the marine plastic pollution problem is to eventually be resolved. Governments cannot accomplish this task on their own, and will need help and initiative from the public. Moreover, resolving this long-standing problem will require time, money, and energy from many individuals now living and those of future generations, if a safer and cleaner marine environment is to be achieved.
Benthic plastic debris in marine and fresh water environments.
Corcoran, Patricia L
2015-08-01
This review provides a discussion of the published literature concerning benthic plastic debris in ocean, sea, lake, estuary and river bottoms throughout the world. Although numerous investigations of shoreline, surface and near-surface plastic debris provide important information on plastic types, distribution, accumulation, and degradation, studies of submerged plastic debris have been sporadic in the past and have become more prominent only recently. The distribution of benthic debris is controlled mainly by combinations of urban proximity and its association with fishing-related activities, geomorphology, hydrological conditions, and river input. High density plastics, biofouled products, polymers with mineral fillers or adsorbed minerals, and plastic-metal composites all have the potential to sink. Once deposited on the bottoms of water basins and channels, plastics are shielded from UV light, thus slowing the degradation process significantly. Investigations of the interactions between benthic plastic debris and bottom-dwelling organisms will help shed light on the potential dangers of submerged plastic litter.
Accumulation and fragmentation of plastic debris in global environments
Barnes, David K. A.; Galgani, Francois; Thompson, Richard C.; Barlaz, Morton
2009-01-01
One of the most ubiquitous and long-lasting recent changes to the surface of our planet is the accumulation and fragmentation of plastics. Within just a few decades since mass production of plastic products commenced in the 1950s, plastic debris has accumulated in terrestrial environments, in the open ocean, on shorelines of even the most remote islands and in the deep sea. Annual clean-up operations, costing millions of pounds sterling, are now organized in many countries and on every continent. Here we document global plastics production and the accumulation of plastic waste. While plastics typically constitute approximately 10 per cent of discarded waste, they represent a much greater proportion of the debris accumulating on shorelines. Mega- and macro-plastics have accumulated in the highest densities in the Northern Hemisphere, adjacent to urban centres, in enclosed seas and at water convergences (fronts). We report lower densities on remote island shores, on the continental shelf seabed and the lowest densities (but still a documented presence) in the deep sea and Southern Ocean. The longevity of plastic is estimated to be hundreds to thousands of years, but is likely to be far longer in deep sea and non-surface polar environments. Plastic debris poses considerable threat by choking and starving wildlife, distributing non-native and potentially harmful organisms, absorbing toxic chemicals and degrading to micro-plastics that may subsequently be ingested. Well-established annual surveys on coasts and at sea have shown that trends in mega- and macro-plastic accumulation rates are no longer uniformly increasing: rather stable, increasing and decreasing trends have all been reported. The average size of plastic particles in the environment seems to be decreasing, and the abundance and global distribution of micro-plastic fragments have increased over the last few decades. However, the environmental consequences of such microscopic debris are still poorly understood. PMID:19528051
Accumulation and fragmentation of plastic debris in global environments.
Barnes, David K A; Galgani, Francois; Thompson, Richard C; Barlaz, Morton
2009-07-27
One of the most ubiquitous and long-lasting recent changes to the surface of our planet is the accumulation and fragmentation of plastics. Within just a few decades since mass production of plastic products commenced in the 1950s, plastic debris has accumulated in terrestrial environments, in the open ocean, on shorelines of even the most remote islands and in the deep sea. Annual clean-up operations, costing millions of pounds sterling, are now organized in many countries and on every continent. Here we document global plastics production and the accumulation of plastic waste. While plastics typically constitute approximately 10 per cent of discarded waste, they represent a much greater proportion of the debris accumulating on shorelines. Mega- and macro-plastics have accumulated in the highest densities in the Northern Hemisphere, adjacent to urban centres, in enclosed seas and at water convergences (fronts). We report lower densities on remote island shores, on the continental shelf seabed and the lowest densities (but still a documented presence) in the deep sea and Southern Ocean. The longevity of plastic is estimated to be hundreds to thousands of years, but is likely to be far longer in deep sea and non-surface polar environments. Plastic debris poses considerable threat by choking and starving wildlife, distributing non-native and potentially harmful organisms, absorbing toxic chemicals and degrading to micro-plastics that may subsequently be ingested. Well-established annual surveys on coasts and at sea have shown that trends in mega- and macro-plastic accumulation rates are no longer uniformly increasing: rather stable, increasing and decreasing trends have all been reported. The average size of plastic particles in the environment seems to be decreasing, and the abundance and global distribution of micro-plastic fragments have increased over the last few decades. However, the environmental consequences of such microscopic debris are still poorly understood.
Thermal regeneration of an electrochemical concentration cell
Krumpelt, M.; Bates, J.K.
1980-05-09
A system and method are described for thermally regenerating an electrochemical concentration cell having first and second aluminum electrodes respectively positioned in contact with first and second electrolytes separated by an ion exchange member, the first and second electrolytes being composed of different concentrations of an ionic solvent and a salt, preferably an aluminum halide. The ionic solvent may be either organic or inorganic with a relatively low melting point, the ionic solvent and the salt form a complex wherein the free energy of formation of said complex is less than about -5 kcal/mole. A distillation column using solar heat or low grade industrial waste heat receives the first and second electrolytes and thermally decomposes the salt-solvent complex to provide feed material for the two half cells.
Bi, Wentao; Tian, Minglei; Row, Kyung Ho
2012-01-01
This study highlighted the application of a two-stepped extraction method for extraction and separation of oxymatrine from Sophora flavescens Ait. extract by utilizing silica-confined ionic liquids as sorbent. The optimized silica-confined ionic liquid was firstly mixed with plant extract to adsorb oxymatrine. Simultaneously, some interference, such as matrine, was removed. The obtained suspension was then added to a cartridge for solid phase extraction. Through these two steps, target compound was adequately separated from interferences with 93.4% recovery. In comparison with traditional solid phase extraction, this method accelerates loading and reduces the use of organic solvents during washing. Moreover, the optimization of loading volume was simplified as optimization of solid/liquid ratio. Copyright © 2011 Elsevier B.V. All rights reserved.
A self-forming composite electrolyte for solid-state sodium battery with ultra-long cycle life
Zhang, Zhizhen; Yang, Xiao -Qing; Zhang, Qinghua; ...
2016-10-31
Replacing organic liquid electrolyte with inorganic solid electrolytes (SE) can potentially address the inherent safety problems in conventional rechargeable batteries. Furthermore, all-solid-state batteries have been plagues by the relatively low ionic conductivity of solid electrolytes and large charge-transfer resistance resulted from solid-solid interfaces between electrode materials and solid electrolytes. Here we report a new design strategy for improving the ionic conductivity of solid electrolyte by self-forming a composite material. An optimized Na + ion conducting composite electrolyte derived from the NASICON structure was successfully synthesized, yielding ultra-high ionic conductivity of 3.4 mS cm –1 at 25°C and 14 ms cmmore » –1 at 80°C.« less
Oceanic barnacles act as foundation species on plastic debris: implications for marine dispersal.
Gil, Michael A; Pfaller, Joseph B
2016-01-27
Plastic has emerged as an abundant, stable substratum for oceanic dispersal of organisms via rafting. However, the ecological mechanisms underlying community diversity on plastic debris remain poorly understood. On a cruise from California to Hawai'i, we surveyed plastic debris, some likely originating from the 2011 Tōhoku tsunami, to examine the relationship between rafting community diversity and both habitat area and stalked barnacle (Lepas spp.) abundance. For sessile taxa richness, we observed an interaction in which the positive effect of debris area weakened the negative effect of barnacle cover. In contrast, for mobile taxa richness, including cohabiting species from opposite sides of the Pacific Ocean, barnacle abundance had a positive effect that was strongest at smaller debris sizes. These findings suggest that barnacles, through interactions with habitat area, have trait-dependent effects on other species, serving as both foundation species and competitors, mediating the diversity and dispersal potential of marine organisms on plastic debris.
Oceanic barnacles act as foundation species on plastic debris: implications for marine dispersal
Gil, Michael A.; Pfaller, Joseph B.
2016-01-01
Plastic has emerged as an abundant, stable substratum for oceanic dispersal of organisms via rafting. However, the ecological mechanisms underlying community diversity on plastic debris remain poorly understood. On a cruise from California to Hawai’i, we surveyed plastic debris, some likely originating from the 2011 Tōhoku tsunami, to examine the relationship between rafting community diversity and both habitat area and stalked barnacle (Lepas spp.) abundance. For sessile taxa richness, we observed an interaction in which the positive effect of debris area weakened the negative effect of barnacle cover. In contrast, for mobile taxa richness, including cohabiting species from opposite sides of the Pacific Ocean, barnacle abundance had a positive effect that was strongest at smaller debris sizes. These findings suggest that barnacles, through interactions with habitat area, have trait-dependent effects on other species, serving as both foundation species and competitors, mediating the diversity and dispersal potential of marine organisms on plastic debris. PMID:26813348
Kulprathipanja, Santi; Kulkarni, Sudhir S.; Funk, Edward W.
1988-01-01
A multicomponent membrane which may be used for separating various components which are present in a fluid feed mixture comprises a mixture of a plasticizer such as a glycol and an organic polymer cast upon a porous organic polymer support. The membrane may be prepared by casting an emulsion or a solution of the plasticizer and polymer on the porous support, evaporating the solvent and recovering the membrane after curing.
Stankus, Dylan P; Lohse, Samuel E; Hutchison, James E; Nason, Jeffrey A
2011-04-15
The adsorption of natural organic matter (NOM) to the surfaces of natural colloids and engineered nanoparticles is known to strongly influence, and in some cases control, their surface properties and aggregation behavior. As a result, the understanding of nanoparticle fate, transport, and toxicity in natural systems must include a fundamental framework for predicting such behavior. Using a suite of gold nanoparticles (AuNPs) with different capping agents, the impact of surface functionality, presence of natural organic matter, and aqueous chemical composition (pH, ionic strength, and background electrolytes) on the surface charge and colloidal stability of each AuNP type was investigated. Capping agents used in this study were as follows: anionic (citrate and tannic acid), neutral (2,2,2-[mercaptoethoxy(ethoxy)]ethanol and polyvinylpyrrolidone), and cationic (mercaptopentyl(trimethylammonium)). Each AuNP type appeared to adsorb Suwannee River Humic Acid (SRHA) as evidenced by measurable decreases in zeta potential in the presence of 5 mg C L(-1) SRHA. It was found that 5 mg C L(-1) SRHA provided a stabilizing effect at low ionic strength and in the presence of only monovalent ions while elevated concentrations of divalent cations lead to enhanced aggregation. The colloidal stability of the NPs in the absence of NOM is a function of capping agent, pH, ionic strength, and electrolyte valence. In the presence of NOM at the conditions examined in this study, the capping agent is a less important determinant of stability, and the adsorption of NOM is a controlling factor.
Molecular signatures of plastic phenotypes in two eusocial insect species with simple societies.
Patalano, Solenn; Vlasova, Anna; Wyatt, Chris; Ewels, Philip; Camara, Francisco; Ferreira, Pedro G; Asher, Claire L; Jurkowski, Tomasz P; Segonds-Pichon, Anne; Bachman, Martin; González-Navarrete, Irene; Minoche, André E; Krueger, Felix; Lowy, Ernesto; Marcet-Houben, Marina; Rodriguez-Ales, Jose Luis; Nascimento, Fabio S; Balasubramanian, Shankar; Gabaldon, Toni; Tarver, James E; Andrews, Simon; Himmelbauer, Heinz; Hughes, William O H; Guigó, Roderic; Reik, Wolf; Sumner, Seirian
2015-11-10
Phenotypic plasticity is important in adaptation and shapes the evolution of organisms. However, we understand little about what aspects of the genome are important in facilitating plasticity. Eusocial insect societies produce plastic phenotypes from the same genome, as reproductives (queens) and nonreproductives (workers). The greatest plasticity is found in the simple eusocial insect societies in which individuals retain the ability to switch between reproductive and nonreproductive phenotypes as adults. We lack comprehensive data on the molecular basis of plastic phenotypes. Here, we sequenced genomes, microRNAs (miRNAs), and multiple transcriptomes and methylomes from individual brains in a wasp (Polistes canadensis) and an ant (Dinoponera quadriceps) that live in simple eusocial societies. In both species, we found few differences between phenotypes at the transcriptional level, with little functional specialization, and no evidence that phenotype-specific gene expression is driven by DNA methylation or miRNAs. Instead, phenotypic differentiation was defined more subtly by nonrandom transcriptional network organization, with roles in these networks for both conserved and taxon-restricted genes. The general lack of highly methylated regions or methylome patterning in both species may be an important mechanism for achieving plasticity among phenotypes during adulthood. These findings define previously unidentified hypotheses on the genomic processes that facilitate plasticity and suggest that the molecular hallmarks of social behavior are likely to differ with the level of social complexity.
Molecular signatures of plastic phenotypes in two eusocial insect species with simple societies
Patalano, Solenn; Vlasova, Anna; Wyatt, Chris; Ewels, Philip; Camara, Francisco; Ferreira, Pedro G.; Asher, Claire L.; Jurkowski, Tomasz P.; Segonds-Pichon, Anne; Bachman, Martin; González-Navarrete, Irene; Minoche, André E.; Krueger, Felix; Lowy, Ernesto; Marcet-Houben, Marina; Rodriguez-Ales, Jose Luis; Nascimento, Fabio S.; Balasubramanian, Shankar; Gabaldon, Toni; Tarver, James E.; Andrews, Simon; Himmelbauer, Heinz; Hughes, William O. H.; Guigó, Roderic; Reik, Wolf; Sumner, Seirian
2015-01-01
Phenotypic plasticity is important in adaptation and shapes the evolution of organisms. However, we understand little about what aspects of the genome are important in facilitating plasticity. Eusocial insect societies produce plastic phenotypes from the same genome, as reproductives (queens) and nonreproductives (workers). The greatest plasticity is found in the simple eusocial insect societies in which individuals retain the ability to switch between reproductive and nonreproductive phenotypes as adults. We lack comprehensive data on the molecular basis of plastic phenotypes. Here, we sequenced genomes, microRNAs (miRNAs), and multiple transcriptomes and methylomes from individual brains in a wasp (Polistes canadensis) and an ant (Dinoponera quadriceps) that live in simple eusocial societies. In both species, we found few differences between phenotypes at the transcriptional level, with little functional specialization, and no evidence that phenotype-specific gene expression is driven by DNA methylation or miRNAs. Instead, phenotypic differentiation was defined more subtly by nonrandom transcriptional network organization, with roles in these networks for both conserved and taxon-restricted genes. The general lack of highly methylated regions or methylome patterning in both species may be an important mechanism for achieving plasticity among phenotypes during adulthood. These findings define previously unidentified hypotheses on the genomic processes that facilitate plasticity and suggest that the molecular hallmarks of social behavior are likely to differ with the level of social complexity. PMID:26483466
NASA Astrophysics Data System (ADS)
Taniguchi, Kouji; Narushima, Keisuke; Yamagishi, Kayo; Shito, Nanami; Kosaka, Wataru; Miyasaka, Hitoshi
2017-06-01
Electrical magnetism control is realized in a Li-ion battery system through a redox reaction involving ion migrations; “magneto-ionic control”. A quasi-layered metal-organic framework compound with a cross-linked π-conjugated/unconjugated one-dimensional chain motifs composed of electron-donor/acceptor units is developed as the cathode material. A change in magnetic phase from paramagnetic to ferrimagnetic is demonstrated by means of electron-filling control for the acceptor units via insertion of Li+-ions into pores in the material. The transition temperature is as high as that expected for highly π-conjugated layered systems, indicating an extension of π-conjugated exchange paths by rearranging coordination bonds in the first discharge process.
Epigenetic Potential as a Mechanism of Phenotypic Plasticity in Vertebrate Range Expansions.
Kilvitis, Holly J; Hanson, Haley; Schrey, Aaron W; Martin, Lynn B
2017-08-01
During range expansions, organisms are often exposed to multiple pressures, including novel enemies (i.e., predators, competitors and/or parasites) and unfamiliar or limited resources. Additionally, small propagule sizes at range edges can result in genetic founder effects and bottlenecks, which can affect phenotypic diversity and thus selection. Despite these obstacles, individuals in expanding populations often thrive at the periphery of a range, and this success may be mediated by phenotypic plasticity. Increasing evidence suggests that epigenetic mechanisms may underlie such plasticity because they allow for more rapid phenotypic responses to novel environments than are possible via the accumulation of genetic variation. Here, we review how molecular epigenetic mechanisms could facilitate plasticity in range-expanding organisms, emphasizing the roles of DNA methylation and other epigenetic marks in the physiological regulatory networks that drive whole-organism performance. We focus on the hypothalamic-pituitary-adrenal (HPA) axis, arguing that epigenetically-mediated plasticity in the regulation of glucocorticoids in particular might strongly impact range expansions. We hypothesize that novel environments release and/or select for epigenetic potential in HPA variation and hence organismal performance and ultimately fitness. © The Author 2017. Published by Oxford University Press on behalf of the Society for Integrative and Comparative Biology. All rights reserved. For permissions please email: journals.permissions@oup.com.
Transgenerational plasticity and climate change experiments: Where do we go from here?
Donelson, Jennifer M; Salinas, Santiago; Munday, Philip L; Shama, Lisa N S
2018-01-01
Phenotypic plasticity, both within and across generations, is an important mechanism that organisms use to cope with rapid climate change. While an increasing number of studies show that plasticity across generations (transgenerational plasticity or TGP) may occur, we have limited understanding of key aspects of TGP, such as the environmental conditions that may promote it, its relationship to within-generation plasticity (WGP) and its role in evolutionary potential. In this review, we consider how the detection of TGP in climate change experiments is affected by the predictability of environmental variation, as well as the timing and magnitude of environmental change cues applied. We also discuss the need to design experiments that are able to distinguish TGP from selection and TGP from WGP in multigenerational experiments. We conclude by suggesting future research directions that build on the knowledge to date and admit the limitations that exist, which will depend on the way environmental change is simulated and the type of experimental design used. Such an approach will open up this burgeoning area of research to a wider variety of organisms and allow better predictive capacity of the role of TGP in the response of organisms to future climate change. © 2017 John Wiley & Sons Ltd.
Advances in sensing and biosensing of bisphenols: A review.
Dhanjai; Sinha, Ankita; Wu, Lingxia; Lu, Xianbo; Chen, Jiping; Jain, Rajeev
2018-01-15
Bisphenols (BPs) are well known endocrine disrupting chemicals (EDCs) that cause adverse effects on the environment, biotic life and human health. BPs have been studied extensively because of an increasing concern for the safety of the environment and for human health. They are major raw materials for manufacturing polycarbonates, thermal papers and epoxy resins and are considered hazardous environmental contaminants. A vast array of sensors and biosensors have been developed for the sensitive screening of BPs based on carbon nanomaterials (carbon nanotubes, fullerenes, graphene and graphene oxide), quantum dots, metal and metal oxide nanocomposites, polymer nanocomposites, metal organic frameworks, ionic liquids and molecularly imprinted polymers. This review is devoted mainly to a variety of sensitive, selective and reliable sensing and biosensing methods for the detection of BPs using electrochemistry, fluorescence, colorimetry, surface plasmon resonance, luminescence, ELISAs, circular dichroism, resonance Rayleigh scattering and adsorption techniques in plastic products, food samples, food packaging, industrial wastes, pharmaceutical products, human body fluids and many other matrices. It summarizes the advances in sensing and biosensing methods for the detection of BPs since 2010. Furthermore, the article discusses challenges and future perspectives in the development of novel sensing methods for the detection of BP analogs. Copyright © 2017 Elsevier B.V. All rights reserved.
Development of composite membranes of PVA-TEOS doped KOH for alkaline membrane fuel cell
NASA Astrophysics Data System (ADS)
Haryadi, Sugianto, D.; Ristopan, E.
2015-12-01
Anion exchange membranes (AEMs) play an important role in separating fuel and oxygen (or air) in the Alkaline Membrane Fuel Cells. Preparation of hybrid organic inorganic materials of Polyvinylalcohol (PVA) - Tetraethylorthosilicate (TEOS) composite membrane doped KOH for direct alcohol alkaline fuel cell application has been investigated. The sol-gel method has been used to prepare the composite membrane of PVA-TEOS through crosslinking step and catalyzed by concentrated of hydrochloric acid. The gel solution was cast on the membrane plastic plate to obtain membrane sheets. The dry membranes were then doped by immersing in various concentrations of KOH solutions for about 4 hours. Investigations of the cross-linking process and the presence of hydroxyl group were conducted by FTIR as shown for frequency at about 1600 cm-1 and 3300 cm-1 respectively. The degree of swelling in ethanol decreased as the KOH concentration for membrane soaking process increased. The ion exchange capacity (IEC) of the membrane was 0.25meq/g. This composite membranes display significant ionic conductivity of 3.23 x 10-2 S/cm in deionized water at room temperature. In addition, the morphology observation by scanning electron microscope (SEM) of the membrane indicates that soaking process of membrane in KOH increased thermal resistant.
Plastic responses of bryozoans to ocean acidification.
Swezey, Daniel S; Bean, Jessica R; Hill, Tessa M; Gaylord, Brian; Ninokawa, Aaron T; Sanford, Eric
2017-12-01
Phenotypic plasticity has the potential to allow organisms to respond rapidly to global environmental change, but the range and effectiveness of these responses are poorly understood across taxa and growth strategies. Colonial organisms might be particularly resilient to environmental stressors, as organizational modularity and successive asexual generations can allow for distinctively flexible responses in the aggregate form. We performed laboratory experiments to examine the effects of increasing dissolved carbon dioxide (CO 2 ) (i.e. ocean acidification) on the colonial bryozoan Celleporella cornuta sampled from two source populations within a coastal upwelling region of the northern California coast. Bryozoan colonies were remarkably plastic under these CO 2 treatments. Colonies raised under high CO 2 grew more quickly, investing less in reproduction and producing lighter skeletons when compared with genetically identical clones raised under current surface atmosphere CO 2 values. Bryozoans held under high CO 2 conditions also changed the Mg/Ca ratio of skeletal calcite and increased the expression of organic coverings in new growth, which may serve as protection against acidified water. We also observed strong differences between source populations in reproductive investment and organic covering reaction norms, consistent with adaptive responses to persistent spatial variation in local oceanographic conditions. Our results demonstrate that phenotypic plasticity and energetic trade-offs can mediate biological responses to global environmental change, and highlight the broad range of strategies available to colonial organisms. © 2017. Published by The Company of Biologists Ltd.
Eco-Evo-Devo: developmental symbiosis and developmental plasticity as evolutionary agents.
Gilbert, Scott F; Bosch, Thomas C G; Ledón-Rettig, Cristina
2015-10-01
The integration of research from developmental biology and ecology into evolutionary theory has given rise to a relatively new field, ecological evolutionary developmental biology (Eco-Evo-Devo). This field integrates and organizes concepts such as developmental symbiosis, developmental plasticity, genetic accommodation, extragenic inheritance and niche construction. This Review highlights the roles that developmental symbiosis and developmental plasticity have in evolution. Developmental symbiosis can generate particular organs, can produce selectable genetic variation for the entire animal, can provide mechanisms for reproductive isolation, and may have facilitated evolutionary transitions. Developmental plasticity is crucial for generating novel phenotypes, facilitating evolutionary transitions and altered ecosystem dynamics, and promoting adaptive variation through genetic accommodation and niche construction. In emphasizing such non-genomic mechanisms of selectable and heritable variation, Eco-Evo-Devo presents a new layer of evolutionary synthesis.
Srinivasa, Narayan; Jiang, Qin
2013-01-01
This study describes a spiking model that self-organizes for stable formation and maintenance of orientation and ocular dominance maps in the visual cortex (V1). This self-organization process simulates three development phases: an early experience-independent phase, a late experience-independent phase and a subsequent refinement phase during which experience acts to shape the map properties. The ocular dominance maps that emerge accommodate the two sets of monocular inputs that arise from the lateral geniculate nucleus (LGN) to layer 4 of V1. The orientation selectivity maps that emerge feature well-developed iso-orientation domains and fractures. During the last two phases of development the orientation preferences at some locations appear to rotate continuously through ±180° along circular paths and referred to as pinwheel-like patterns but without any corresponding point discontinuities in the orientation gradient maps. The formation of these functional maps is driven by balanced excitatory and inhibitory currents that are established via synaptic plasticity based on spike timing for both excitatory and inhibitory synapses. The stability and maintenance of the formed maps with continuous synaptic plasticity is enabled by homeostasis caused by inhibitory plasticity. However, a prolonged exposure to repeated stimuli does alter the formed maps over time due to plasticity. The results from this study suggest that continuous synaptic plasticity in both excitatory neurons and interneurons could play a critical role in the formation, stability, and maintenance of functional maps in the cortex. PMID:23450808
Synthetic polymers in the marine environment: a rapidly increasing, long-term threat.
Moore, Charles James
2008-10-01
Synthetic polymers, commonly known as plastics, have been entering the marine environment in quantities paralleling their level of production over the last half century. However, in the last two decades of the 20th Century, the deposition rate accelerated past the rate of production, and plastics are now one of the most common and persistent pollutants in ocean waters and beaches worldwide. Thirty years ago the prevailing attitude of the plastic industry was that "plastic litter is a very small proportion of all litter and causes no harm to the environment except as an eyesore" [Derraik, J.G.B., 2002. The pollution of the marine environment by plastic debris: a review. Mar. Pollut. Bull. 44(9), 842-852]. Between 1960 and 2000, the world production of plastic resins increased 25-fold, while recovery of the material remained below 5%. Between 1970 and 2003, plastics became the fastest growing segment of the US municipal waste stream, increasing nine-fold, and marine litter is now 60-80% plastic, reaching 90-95% in some areas. While undoubtedly still an eyesore, plastic debris today is having significant harmful effects on marine biota. Albatross, fulmars, shearwaters and petrels mistake floating plastics for food, and many individuals of these species are affected; in fact, 44% of all seabird species are known to ingest plastic. Sea turtles ingest plastic bags, fishing line and other plastics, as do 26 species of cetaceans. In all, 267 species of marine organisms worldwide are known to have been affected by plastic debris, a number that will increase as smaller organisms are assessed. The number of fish, birds, and mammals that succumb each year to derelict fishing nets and lines in which they become entangled cannot be reliably known; but estimates are in the millions. We divide marine plastic debris into two categories: macro, >5 mm and micro, <5 mm. While macro-debris may sometimes be traced to its origin by object identification or markings, micro-debris, consisting of particles of two main varieties, (1) fragments broken from larger objects, and (2) resin pellets and powders, the basic thermoplastic industry feedstocks, are difficult to trace. Ingestion of plastic micro-debris by filter feeders at the base of the food web is known to occur, but has not been quantified. Ingestion of degraded plastic pellets and fragments raises toxicity concerns, since plastics are known to adsorb hydrophobic pollutants. The potential bioavailability of compounds added to plastics at the time of manufacture, as well as those adsorbed from the environment are complex issues that merit more widespread investigation. The physiological effects of any bioavailable compounds desorbed from plastics by marine biota are being directly investigated, since it was found 20 years ago that the mass of ingested plastic in Great Shearwaters was positively correlated with PCBs in their fat and eggs. Colonization of plastic marine debris by sessile organisms provides a vector for transport of alien species in the ocean environment and may threaten marine biodiversity. There is also potential danger to marine ecosystems from the accumulation of plastic debris on the sea floor. The accumulation of such debris can inhibit gas exchange between the overlying waters and the pore waters of the sediments, and disrupt or smother inhabitants of the benthos. The extent of this problem and its effects have recently begun to be investigated. A little more than half of all thermoplastics will sink in seawater.
A methodology for developing remediation goals for sites with contaminated sediments is provided. The remediation goals are based upon the concentrations of chemicals in the sediment interstitial water measured using the passive sampling technique. The passive sampling technique ...
Li, Zhenhan; Xia, Shanhong; Wang, Jinfen; Bian, Chao; Tong, Jianhua
2016-01-15
A novel method for determination of trace mercury in water is developed. The method is performed by extracting mercury firstly with ionic liquids (ILs) and then detecting the concentration of mercury in organic media with anodic stripping voltammetry. Liquid-liquid extraction of mercury(II) ions by four ionic liquids with N-octylpyridinium cations ([OPy](+)) was studied. N-octylpyridinium tetrafluoroborate and N-octylpyridinium trifluoromethylsulfonate were found to be efficient and selective extractant for mercury. Temperature controlled dispersive liquid phase microextraction (TC-DLPME) technique was utilized to improve the performance of preconcentration. After extraction, precipitated IL was diluted by acetonitrile buffer and mercury was detected by differential pulse stripping voltammetry (DPSV) with gold disc electrode. Mercury was enriched by 17 times while interfering ions were reduced by two orders of magnitude in the organic media under optimum condition. Sensitivity and selectivity for electrochemical determination of mercury were improved by using the proposed method. Tap, pond and waste water samples were analyzed with recoveries ranging from 81% to 107% and detection limit of 0.05 μg/L. Copyright © 2015 Elsevier B.V. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Zavgorodnya, Oleksandra; Shamshina, Julia L.; Bonner, Jonathan R.
Here, we report the correlation between key solution properties and spinability of chitin from the ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate ([C 2mim][OAc]), and the similarities and differences to electrospinning solutions of non-ionic polymers in volatile organic compounds (VOCs). We found that when electrospinning is conducted from ILs, conductivity and surface tension are not the key parameters regulating spinability, while solution viscosity and polymer concentration are. Contrarily, for electrospinning of polymers from VOCs, solution conductivity and viscosity have been reported to be among some of the most important factors controlling fiber formation. For chitin electrospun from [C 2mim][OAc], we found bothmore » a critical chitin concentration required for continuous fiber formation (> 0.20 wt%) and a required viscosity for the spinning solution (between ca. 450 – 1500 cP). The high viscosities of the biopolymer-IL solutions made it possible to electrospin solutions with low, less than 1 wt% of polymer concentration and produce thin fibers without the need to adjust the electrospinning parameters. These results suggest new prospects for the control of fiber architecture in non-woven mats, which is crucial for materials performance.« less
Zavgorodnya, Oleksandra; Shamshina, Julia L.; Bonner, Jonathan R.; ...
2017-04-27
Here, we report the correlation between key solution properties and spinability of chitin from the ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate ([C 2mim][OAc]), and the similarities and differences to electrospinning solutions of non-ionic polymers in volatile organic compounds (VOCs). We found that when electrospinning is conducted from ILs, conductivity and surface tension are not the key parameters regulating spinability, while solution viscosity and polymer concentration are. Contrarily, for electrospinning of polymers from VOCs, solution conductivity and viscosity have been reported to be among some of the most important factors controlling fiber formation. For chitin electrospun from [C 2mim][OAc], we found bothmore » a critical chitin concentration required for continuous fiber formation (> 0.20 wt%) and a required viscosity for the spinning solution (between ca. 450 – 1500 cP). The high viscosities of the biopolymer-IL solutions made it possible to electrospin solutions with low, less than 1 wt% of polymer concentration and produce thin fibers without the need to adjust the electrospinning parameters. These results suggest new prospects for the control of fiber architecture in non-woven mats, which is crucial for materials performance.« less
On the acid-base properties of humic acid in soil.
Cooke, James D; Hamilton-Taylor, John; Tipping, Edward
2007-01-15
Humic acid was isolated from three contrasting organic-rich soils and acid-base titrations performed over a range of ionic strengths. Results obtained were unlike most humic acid data sets; they showed a greater ionic strength dependency at low pH than at high pH. Forward- and back-titrations with the base and acid revealed hysteresis, particularly at low pH. Previous authors attributed this type of hysteresis to humic acid aggregates-created during the isolation procedure-being redissolved during titration as the pH increased and regarded the results as artificial. However, forward- and back-titrations with organic-rich soils also demonstrated a similar hysteretic behavior. These observations indicate (i) that titrations of humic acid in aggregated form (as opposed to the more usual dissolved form) are more representative of the acid-base properties of humic acid in soil and (ii) that the ionic strength dependency of proton binding in humic acid is related to its degree of aggregation. Thus, the current use of models based on data from dissolved humic substances to predictthe acid-base properties of humic acid in soil under environmental conditions may be flawed and could substantially overestimate their acid buffering capacity.
Yang, Xinyao; Lin, Shihong; Wiesner, Mark R
2014-01-15
Interactions between organic matter (OM) and engineered polymer coatings as they affect the retention of polyvinylpyrrolidone (PVP) polymer-coated silver nanoparticles (AgNPs) were studied. Two distinct types of OM-cysteine representing low molecular weight multivalent functional groups, and Suwannee River Humic Acid (HA) representing high molecular weight polymers, were investigated with respect to their effects on particle stability in aggregation and deposition. Aggregation of the PVP coated AgNPs (PVP-AgNPs) was enhanced by cysteine addition at high ionic strengths, which was attributed to cysteine binding to the AgNPs and replacing the otherwise steric stabilizing agent PVP. In contrast the addition of HA did not increase aggregation rates and decreased PVP-AgNP deposition to the silica porous medium, consistent with enhanced electrosteric stabilization by the HA. Although cysteine also reduced deposition in the porous medium, the mechanisms of reduced deposition appear to be enhanced electric double layer (EDL) interaction at low ionic strengths. At higher ionic strengths, aggregation was favored leading to lower deposition due to smaller diffusion coefficients and single collector efficiencies despite the reduced EDL interactions. Copyright © 2013 Elsevier B.V. All rights reserved.
Huang, Liangfang; Wang, Wenmin; Wei, Xiaoqin; Wei, Haiyan
2015-04-23
The hydrosilylation of unsaturated carbon-heteroatom (C═O, C═N) bonds catalyzed by high-valent rhenium(V)-dioxo complex ReO2I(PPh3)2 (1) were studied computationally to determine the underlying mechanism. Our calculations revealed that the ionic outer-sphere pathway in which the organic substrate attacks the Si center in an η(1)-silane rhenium adduct to prompt the heterolytic cleavage of the Si-H bond is the most energetically favorable process for rhenium(V)-dioxo complex 1 catalyzed hydrosilylation of imines. The activation energy of the turnover-limiting step was calculated to be 22.8 kcal/mol with phenylmethanimine. This value is energetically more favorable than the [2 + 2] addition pathway by as much as 10.0 kcal/mol. Moreover, the ionic outer-sphere pathway competes with the [2 + 2] addition mechanism for rhenium(V)-dioxo complex 1 catalyzing the hydrosilylation of carbonyl compounds. Furthermore, the electron-donating group on the organic substrates would induce a better activity favoring the ionic outer-sphere mechanistic pathway. These findings highlight the unique features of high-valent transition-metal complexes as Lewis acids in activating the Si-H bond and catalyzing the reduction reactions.
"Solvent-in-salt" systems for design of new materials in chemistry, biology and energy research.
Azov, Vladimir A; Egorova, Ksenia S; Seitkalieva, Marina M; Kashin, Alexey S; Ananikov, Valentine P
2018-02-21
Inorganic and organic "solvent-in-salt" (SIS) systems have been known for decades but have attracted significant attention only recently. Molten salt hydrates/solvates have been successfully employed as non-flammable, benign electrolytes in rechargeable lithium-ion batteries leading to a revolution in battery development and design. SIS with organic components (for example, ionic liquids containing small amounts of water) demonstrate remarkable thermal stability and tunability, and present a class of admittedly safer electrolytes, in comparison with traditional organic solvents. Water molecules tend to form nano- and microstructures (droplets and channel networks) in ionic media impacting their heterogeneity. Such microscale domains can be employed as microreactors for chemical and enzymatic synthesis. In this review, we address known SIS systems and discuss their composition, structure, properties and dynamics. Special attention is paid to the current and potential applications of inorganic and organic SIS systems in energy research, chemistry and biochemistry. A separate section of this review is dedicated to experimental methods of SIS investigation, which is crucial for the development of this field.
Design of Bioactive Organic-inorganic Hybrid Materials with Self-setting Ability
NASA Astrophysics Data System (ADS)
Miyazaki, T.; Machida, S.; Morita, Y.; Ishida, E.
2011-10-01
Paste-like materials with ability of self-setting are attractive for bone substitutes, since they can be injected from the small hole with minimized invasion to the patient. Although bone cements which set as apatite are clinically used, there is limitation on clinical applications due to their mechanical properties such as high brittleness and low fracture toughness. To overcome this problem, organic-inorganic hybrids based on a flexible polymer are attractive. We have obtained an idea for design of self-setting hybrids using polyion complex fabricated by ionic interaction of anionic and cationic polymers. We aimed at preparation of organic-inorganic hybrids exhibiting self-setting ability and bioactivity. The liquid component was prepared from cationic chitosan aqueous solution. The powder component was prepared by mixing various carrageenans with α-tricalcium phosphate (α-TCP). The obtained cements set within 1 day. Compressive strength showed tendency to increase with increase in α-TCP content in the powder component. The prepared cements formed the apatite in simulated body fluid within 3 days. Novel self-setting materials based on organic-inorganic hybrid can be designed utilizing ionic interaction of polysaccharide.
Accumulation of plastic-derived chemicals in tissues of seabirds ingesting marine plastics.
Tanaka, Kosuke; Takada, Hideshige; Yamashita, Rei; Mizukawa, Kaoruko; Fukuwaka, Masa-aki; Watanuki, Yutaka
2013-04-15
We analyzed polybrominated diphenyl ethers (PBDEs) in abdominal adipose of oceanic seabirds (short-tailed shearwaters, Puffinus tenuirostris) collected in northern North Pacific Ocean. In 3 of 12 birds, we detected higher-brominated congeners (viz., BDE209 and BDE183), which are not present in the natural prey (pelagic fish) of the birds. The same compounds were present in plastic found in the stomachs of the 3 birds. These data suggested the transfer of plastic-derived chemicals from ingested plastics to the tissues of marine-based organisms. Copyright © 2012 Elsevier Ltd. All rights reserved.
Actinomyces-like organisms in cervical smears from women using intrauterine contraceptive devices.
Duguid, H L; Parratt, D; Traynor, R
1980-01-01
Cervical smears from 293 users of intrauterine contraceptive devices attending family planning clinics in East Fife, Dundee, and Angus were stained by Papanicolaou and Gram's methods and examined for actinomyces-like organisms. Of the 128 women using plastic devices, 40 gave smears positive for these organisms. In contrast only two positive smears were obtained from the 165 women using devices containing copper and none from a control group of 300 women taking oral contraceptives. Colonisation was more common in women whose plastic devices had been in situ for over two years. Correlations between the presence of these organisms and recorded incidences of pain and both clinical and cytological evidence of inflammation of the lower genital tract were highly significant (p = 0.00001, p < 0.00001, and p < 0.00001 respectively). The results suggest that plastic intrauterine contraceptive devices predispose to colonisation by actinomyces-like organisms, particularly after long-term use. Hence if the apparently bacteriostatic action of copper devices is confirmed these should probably be more widely used. Images FIG 1 FIG 2 PMID:7427358
Jenke, Dennis; Couch, Tom; Gillum, Amy
2010-01-01
Material/water equilibrium binding constants (E(b)) were determined for 11 organic solutes and 2 plastic materials commonly used in pharmaceutical product containers (plasticized polyvinyl chloride and polyolefin). In general, solute binding by the plasticized polyvinyl chloride material was greater, by nearly an order of magnitude, than the binding by the polyolefin (on an equal weight basis). The utilization of the binding constants to facilitate container compatibility assessments (e.g., drug loss by container binding) for drug-containing products is discussed.
Modeling of orthotropic plate fracture under impact load using various strength criteria
NASA Astrophysics Data System (ADS)
Radchenko, Andrey; Krivosheina, Marina; Kobenko, Sergei; Radchenko, Pavel; Grebenyuk, Grigory
2017-01-01
The paper presents the comparative analysis of various tensor multinomial criteria of strength for modeling of orthotropic organic plastic plate fracture under impact load. Ashkenazi, Hoffman and Wu strength criteria were used. They allowed fracture modeling of orthotropic materials with various compressive and tensile strength properties. The modeling of organic plastic fracture was performed numerically within the impact velocity range of 700-1500 m/s.
Zhang, Yonghong; Wang, Bin; Zhang, Xiaomei; Huang, Jianbin; Liu, Chenjiang
2015-02-26
We report here an efficient and green method for Biginelli condensation reaction of aldehydes, β-ketoesters and urea or thiourea catalyzed by Brønsted acidic ionic liquid [Btto][p-TSA] under solvent-free conditions. Compared to the classical Biginelli reaction conditions, the present method has the advantages of giving good yields, short reaction times, near room temperature conditions and the avoidance of the use of organic solvents and metal catalyst.
NASA Technical Reports Server (NTRS)
Anicich, V. G.; Huntress, W. T., Jr.
1986-01-01
All bimolecular positive ion-molecule reactions reported from 1965 to 1985 for temperatures below 1000 K are included in the present survey of those ion-molecule reactions pertinent to the chemistries of planetary atmospheres, cometary comae, and interstellar clouds. This survey is intended as an update of the first, by Huntress (1977). The tabular presentation is organized according to reactant ion, with cross-references for both the ionic and the neutral reactants as well as the ionic and neutral products.
Ionically self-assembled monolayers (ISAMs)
NASA Astrophysics Data System (ADS)
Janik, John
2001-04-01
Ionically self-assembled monolayers (ISAMs), fabricated by alternate adsorption of cationic and anionic components, yield exceptionally homogeneous thin films with sub-nanometer control of the thickness and relative special location of the component materials. Using organic electrochromic materials such as polyaniline, we report studies of electrochromic responses in ISAM films. Reversible changes in the absorption spectrum are observed with the application of voltages on the order of 1.0 V. Measurements are made using both liquid electrolytes and in all-solid state devices incorporating solid polyelectrolytes such as poly(2-acylamido 2-methyl propane sulfonic acid) (PAMPS).
2007-01-04
been found to be a suitable means for depositing thin films of chitosan onto the surface of a silicon wafer. A small amount of liquid solution is...response of the system to changes of the meniscus position in the capillary. This was done by gradually filling the working volume with an ionic liquid ...from the wetting of the electrodes by the ionic liquid . From this data we have calculated a signal to noise ratio of 100 for the read out mechanism
Thermophysical Properties of Nanoparticle-Enhanced Ionic Liquids (NEILs) Heat-Transfer Fluids
DOE Office of Scientific and Technical Information (OSTI.GOV)
Fox, Elise B.; Visser, Ann E.; Bridges, Nicholas J.
2013-06-20
An experimental investigation was completed on nanoparticle enhanced ionic liquid heat transfer fluids as an alternative to conventional organic based heat transfer fluids (HTFs). These nanoparticle-based HTFs have the potential to deliver higher thermal conductivity than the base fluid without a significant increase in viscosity at elevated temperatures. The effect of nanoparticle morphology and chemistry on thermophysical properties was examined. Whisker shaped nanomaterials were found to have the largest thermal conductivity temperature dependence and were also less likely to agglomerate in the base fluid than spherical shaped nanomaterials.
Organo-redox shuttle promoted protic ionic liquid electrolyte for supercapacitor
NASA Astrophysics Data System (ADS)
Sathyamoorthi, S.; Suryanarayanan, V.; Velayutham, D.
2015-01-01
Performance of activated charcoal based supercapacitor (SC) containing hydroquinone (HQ), as an organic redox shuttle, is evaluated in triethylammonium bis(trifluoromethane)sulfonimide (TEATFSI). Cyclic voltammograms of the SC show pseudocapacitive contribution of HQ and the galvanostatic charge-discharge measurement shows enhanced specific capacitance (72.0 F g-1) and specific energy (31.22 Wh Kg-1). The presence of HQ shows low charge transfer resistance, as confirmed by electrochemical impedance spectroscopy. Cyclic stability of the SC in the redox mediated electrolyte is comparable with that of the protic ionic liquid.
Synthesis and anti-microbial activity of hydroxylammonium ionic liquids.
Ismail Hossain, M; El-Harbawi, Mohanad; Noaman, Yousr Abdulhadi; Bustam, Mohd Azmi B; Alitheen, Noorjahan Banu Mohamed; Affandi, Nor Azrin; Hefter, Glenn; Yin, Chun-Yang
2011-06-01
Eight hydroxylammonium-based room temperature ionic liquids (ILs) have been synthesized by acid-base neutralization of ethanolamines with organic acids. The ILs were characterized by infrared and nuclear magnetic resonance spectroscopies and elemental analysis. Their anti-microbial activities were determined using the well-diffusion method. All eight ILs were toxic to Staphylococcus aureus, while 2-hydroxyethylammonium lactate and 2-hydroxy-N-(2-hydroxyethyl)-N-methylethanaminium acetate showed high anti-microbial activity against a wide range of human pathogens. Crown Copyright © 2011. Published by Elsevier Ltd. All rights reserved.
Effects of microplastic on fitness and PCB bioaccumulation by the lugworm Arenicola marina (L.).
Besseling, Ellen; Wegner, Anna; Foekema, Edwin M; van den Heuvel-Greve, Martine J; Koelmans, Albert A
2013-01-02
It has been speculated that marine microplastics may cause negative effects on benthic marine organisms and increase bioaccumulation of persistent organic pollutants (POPs). Here, we provide the first controlled study of plastic effects on benthic organisms including transfer of POPs. The effects of polystyrene (PS) microplastic on survival, activity, and bodyweight, as well as the transfer of 19 polychlorinated biphenyls (PCBs), were assessed in bioassays with Arenicola marina (L.). PS was pre-equilibrated in natively contaminated sediment. A positive relation was observed between microplastic concentration in the sediment and both uptake of plastic particles and weight loss by A. marina. Furthermore, a reduction in feeding activity was observed at a PS dose of 7.4% dry weight. A low PS dose of 0.074% increased bioaccumulation of PCBs by a factor of 1.1-3.6, an effect that was significant for ΣPCBs and several individual congeners. At higher doses, bioaccumulation decreased compared to the low dose, which however, was only significant for PCB105. PS had statistically significant effects on the organisms' fitness and bioaccumulation, but the magnitude of the effects was not high. This may be different for sites with different plastic concentrations, or plastics with a higher affinity for POPs.
Chemoreception drives plastic consumption in a hard coral.
Allen, Austin S; Seymour, Alexander C; Rittschof, Daniel
2017-11-15
The drivers behind microplastic (up to 5mm in diameter) consumption by animals are uncertain and impacts on foundational species are poorly understood. We investigated consumption of weathered, unfouled, biofouled, pre-production and microbe-free National Institute of Standards plastic by a scleractinian coral that relies on chemosensory cues for feeding. Experiment one found that corals ingested many plastic types while mostly ignoring organic-free sand, suggesting that plastic contains phagostimulents. Experiment two found that corals ingested more plastic that wasn't covered in a microbial biofilm than plastics that were biofilmed. Additionally, corals retained ~8% of ingested plastic for 24h or more and retained particles appeared stuck in corals, with consequences for energetics, pollutant toxicity and trophic transfer. The potential for chemoreception to drive plastic consumption in marine taxa has implications for conservation. Copyright © 2017 Elsevier Ltd. All rights reserved.
Gauquie, Johanna; Devriese, Lisa; Robbens, Johan; De Witte, Bavo
2015-11-01
Chemical compounds present on plastic were characterised on different types of plastic litter and beached pellets, using a general GC-MS screening method. A variety of plastic related compounds, such as building blocks, antioxidants, additives and degradation products, were identified next to diverse environmental pollutants and biofilm compounds. A validated method for the analysis of PAHs and PCBs on beached pellets at the Belgian Coast, showed concentrations of ∑ 16 EPA-PAHs of 1076-3007 ng g(-1) plastic, while the concentrations of ∑ 7 OSPAR-PCBs ranged from 31 to 236 ng g(-1) plastic. The wide variety of plastic compounds retrieved in the general screening showed the importance of plastic as a potential source of contaminants and their degradation products. Copyright © 2015 Elsevier Ltd. All rights reserved.
Organic electrical double layer transistors gated with ionic liquids
NASA Astrophysics Data System (ADS)
Xie, Wei; Frisbie, C. Daniel
2011-03-01
Transport in organic semiconductors gated with several types of ionic liquids has been systematically studied at charge densities larger than 1013 cm-2 . We observe a pronounced maximum in channel conductance for both p-type and n-type organic single crystals which is attributed to carrier localization at the semiconductor-electrolyte interface. Carrier mobility, as well as charge density and dielectric capacitance are determined through displacement current measurement and capacitance-voltage measurement. By using a larger-sized and spherical anion, tris(pentafluoroethyl)trifluorophosphate (FAP), effective carrier mobility in rubrene can be enhanced substantially up to 3.2 cm2 V-1 s -1 . Efforts have been made to maximize the charge density in rubrene single crystals, and at low temperature when higher gate bias can be applied, charge density can more than double the amount of that at room temperature, reaching 8*1013 cm-2 holes (0.4 holes per rubrene molecule). NSF MRSEC program at the University of Minnesota.
Micellar Electrolytes in Organic Electrochemical Transistors
NASA Astrophysics Data System (ADS)
Cicoira, Fabio; Giuseppe, Tarabella; Nanda, Gaurav; Iannotta, Salvatore; Santato, Clara
2012-02-01
Organic electrochemical transistors (OECTs) are promising for applications in sensing and bioelectronics. OECTs consist of a conducting polymer film (transistor channel) in contact with an electrolyte. A gate electrode immersed in the electrolyte controls the doping/dedoping level of the conducting polymer. OECTs can be operated in aqueous electrolytes, making possible the implementation of organic electronic materials at the interface with biology. The inherent signal amplification of OECTs has the potential to yield sensors with low detection limits and high sensitivity. In this talk we will present recent studies on OECTs using ionic surfactants (such as hexadecyl-trimethyl-ammonium bromide) as electrolytes. As the conducting polymer we used PEDOT:PSS, i.e. (Poly,3-4 ethylenedioxythiopene) doped with Poly(styrene sulphonate). Interestingly, ionic surfactant electrolytes result in large transistor current modulation, especially beyond the critical micellar concentration (CMC). Since micelles play a primary role in biological processes and drug-delivery systems, the use for micellar electrolytes opens new exciting opportunities for the use of OECTs in bioelectronics.
Inorganic-organic separators for alkaline batteries
NASA Technical Reports Server (NTRS)
Sheibley, D. W. (Inventor)
1978-01-01
A flexible separator is reported for use between the electrodes of Ni-Cd and Ni-Zn batteries using alkaline electrolytes. The separator was made by coating a porous substrate with a battery separator composition. The coating material included a rubber-based resin copolymer, a plasticizer and inorganic and organic fillers which comprised 55% by volume or less of the coating as finally dried. One or more of the filler materials, whether organic or inorganic, is preferably active with the alkaline electrolyte to produce pores in the separator coating. The plasticizer was an organic material which is hydrolyzed by the alkaline electrolyte to improve conductivity of the separator coating.
Redman, Aaron D; Parkerton, Thomas F; Butler, Josh David; Letinski, Daniel J; Frank, Richard A; Hewitt, L Mark; Bartlett, Adrienne J; Gillis, Patricia Leigh; Marentette, Julie R; Parrott, Joanne L; Hughes, Sarah A; Guest, Rodney; Bekele, Asfaw; Zhang, Kun; Morandi, Garrett; Wiseman, Steve B; Giesy, John P
2018-06-14
Oil sand operations in Alberta, Canada will eventually include returning treated process-affected waters to the environment. Organic constituents in oil sand process-affected water (OSPW) represent complex mixtures of nonionic and ionic (e.g. naphthenic acids) compounds, and compositions can vary spatially and temporally, which has impeded development of water quality benchmarks. To address this challenge, it was hypothesized that solid phase microextraction fibers coated with polydimethylsiloxane (PDMS) could be used as a biomimetic extraction (BE) to measure bioavailable organics in OSPW. Organic constituents of OSPW were assumed to contribute additively to toxicity, and partitioning to PDMS was assumed to be predictive of accumulation in target lipids, which were the presumed site of action. This method was tested using toxicity data for individual model compounds, defined mixtures, and organic mixtures extracted from OSPW. Toxicity was correlated with BE data, which supports the use of this method in hazard assessments of acute lethality to aquatic organisms. A species sensitivity distribution (SSD), based on target lipid model and BE values, was similar to SSDs based on residues in tissues for both nonionic and ionic organics. BE was shown to be an analytical tool that accounts for bioaccumulation of organic compound mixtures from which toxicity can be predicted, with the potential to aid in the development of water quality guidelines.
Interaction between common organic acids and trace nucleation species in the Earth's atmosphere.
Xu, Yisheng; Nadykto, Alexey B; Yu, Fangqun; Herb, J; Wang, Wei
2010-01-14
Atmospheric aerosols formed via nucleation in the Earth's atmosphere play an important role in the aerosol radiative forcing associated directly with global climate changes and public health. Although it is well-known that atmospheric aerosol particles contain organic species, the chemical nature of and physicochemical processes behind atmospheric nucleation involving organic species remain unclear. In the present work, the interaction of common organic acids with molecular weights of 122, 116, 134, 88, 136, and 150 (benzoic, maleic, malic, pyruvic, phenylacetic, and tartaric acids) with nucleation precursors and charged trace species has been investigated. We found a moderate strong effect of the organic species on the stability of neutral and charged ionic species. In most cases, the free energies of the mixed H(2)SO(4)-organic acid dimer formation are within 1-1.5 kcal mol(-1) of the (H(2)SO(4))(NH(3)) formation energy. The interaction of the organic acids with trace ionic species is quite strong, and the corresponding free energies far exceed those of the (H(3)O(+))(H(2)SO(4)) and (H(3)O(+))(H(2)SO(4))(2) formation. These considerations lead us to conclude that the aforementioned organic acids may possess a substantial capability of stabilizing both neutral and positively charged prenucleation clusters, and thus, they should be studied further with regard to their involvement in the gas-to-particle conversion in the Earth's atmosphere.
Terahertz vibrational modes of the rigid crystal phase of succinonitrile.
Nickel, Daniel V; Delaney, Sean P; Bian, Hongtao; Zheng, Junrong; Korter, Timothy M; Mittleman, Daniel M
2014-04-03
Succinonitrile (N ≡ C-CH2-CH2-C ≡ N), an orientationally disordered molecular plastic crystal at room temperature, exhibits rich phase behavior including a solid-solid phase transition at 238 K. In cooling through this phase transition, the high-temperature rotational disorder of the plastic crystal phase is frozen out, forming a rigid crystal that is both spatially and orientationally ordered. Using temperature-dependent terahertz time-domain spectroscopy, we characterize the vibrational modes of this low-temperature crystalline phase for frequencies from 0.3 to 2.7 THz and temperatures ranging from 20 to 220 K. Vibrational modes are observed at 1.122 and 2.33 THz at 90 K. These modes are assigned by solid-state density functional theory simulations, corresponding respectively to the translation and rotation of the molecules along and about their crystallographic c-axis. In addition, we observe a suppression of the phonon modes as the concentration of dopants, in this case a lithium salt (LiTFSI), increases, indicating the importance of doping-induced disorder in these ionic conductors.
NASA Astrophysics Data System (ADS)
Suleman, M.; Deraman, M.; Othman, M. A. R.; Omar, R.; Hashim, M. A.; Basri, N. H.; Nor, N. S. M.; Dolah, B. N. M.; Hanappi, M. F. Y. M.; Hamdan, E.; Sazali, N. E. S.; Tajuddin, N. S. M.; Jasni, M. R. M.
2016-08-01
We report a novel configuration of symmetrical electric double-layer capacitors (EDLCs) comprising a plastic crystalline succinonitrile (SN) based flexible polymer gel electrolyte, incorporated with sodium trifluoromethane sulfonate (NaTf) immobilised in a host polymer poly (vinylidine fluoride-co-hexafluoropropylene) (PVdF-HFP). The cost-effective activated carbon powder possessing a specific surface area (SSA) of ~ 1700 m2g-1 containing a large proportion of meso-porosity has been derived from tea waste to use as supercapacitor electrodes. The high ionic conductivity (~3.6×10-3 S cm-1 at room temperature) and good electrochemical stability render the gel polymer electrolyte film a suitable candidate for the fabrication of EDLCs. The performance of the EDLCs has been tested by electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and galvanostatic charge-discharge studies. The performance of the EDLC cell is found to be promising in terms of high values of specific capacitance (~270 F g-1), specific energy (~ 36 Wh kg-1), and power density (~ 33 kW kg-1).
NASA Astrophysics Data System (ADS)
Huzaizi, Rahmatina Mohd; Tahir, Syuhada Mohd; Mahbor, Kamisah Mohamad
2017-12-01
Waste cooking oil-based polyol was synthesized using epoxidation and hydroxylation methods. The polyol was combined with 4,4-diphenylmethane diisocyanate to produce polyurethane (PU) to be used as polymer host in solid polymer electrolyte. 30 wt% LiClO4 was added as doping salt and two types of plasticizers were used; ethylene carbonate (PU-EC) and polyethylene glycol (PU-PEG). The SPE films were characterized using Fourier transform infrared spectroscopy, electrochemical impedance spectroscopy, differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The highest conductivity achieved was 8.4 x 10-8 S cm-1 upon addition of 10 wt% EC. The XRD results showed a decrease of crystalline peaks in PU-EC and the increase in PU-PEG. DSC results revealed that the films; PU, PU-EC and PU-PEG had glass transition temperatures of 159.7, 106.0 and 179.7 °C, respectively. The results showed that the addition of EC increased the amorphous region and the free volume in the SPE structure, thus resulted in higher ionic conductivity.
Ozaki, Asako; Kishi, Eri; Ooshima, Tomoko; Hase, Atsushi; Kawamura, Yoko
2016-09-01
Six nanosilver-labelled products and five silver ion (Ag(+))-labelled products were investigated to measure the migration of Ag from food-contact plastics, including nanosilver into various food simulants. The products were obtained in Japanese markets in 2012. Zinc (Zn), another major antimicrobial agent, and three harmful metals, cadmium (Cd), lead (Pb) and arsenic (As), were also examined. Ag and Zn were detected in all six nanosilver products at concentrations of 21-200 and 8.4-140 mg kg(-1), respectively. These metals were also detected in all five Ag(+) products at the same level as nanosilver products. Cd, Pb and As were not detected in any sample. Migrations of Ag and Zn were highest in 4% acetic acid, but also observed in water and 20% ethanol. Big differences were not observed in the migration ratio between nanosilver products and Ag(+) products. The ultrafiltration experiments suggested that the Ag that migrated from nanosilver products into 4% acetic acid was in its ionic form, while that into water and 20% ethanol was in its nanoparticle form.
Notre Dame Geothermal Ionic Liquids Research: Ionic Liquids for Utilization of Geothermal Energy
DOE Office of Scientific and Technical Information (OSTI.GOV)
Brennecke, Joan F.
The goal of this project was to develop ionic liquids for two geothermal energy related applications. The first goal was to design ionic liquids as high temperature heat transfer fluids. We identified appropriate compounds based on both experiments and molecular simulations. We synthesized the new ILs, and measured their thermal stability, measured storage density, viscosity, and thermal conductivity. We found that the most promising compounds for this application are aminopyridinium bis(trifluoromethylsulfonyl)imide based ILs. We also performed some measurements of thermal stability of IL mixtures and used molecular simulations to better understand the thermal conductivity of nanofluids (i.e., mixtures of ILsmore » and nanoparticles). We found that the mixtures do not follow ideal mixture theories and that the addition of nanoparticles to ILs may well have a beneficial influence on the thermal and transport properties of IL-based heat transfer fluids. The second goal was to use ionic liquids in geothermally driven absorption refrigeration systems. We performed copious thermodynamic measurements and modeling of ionic liquid/water systems, including modeling of the absorption refrigeration systems and the resulting coefficients of performance. We explored some IL/organic solvent mixtures as candidates for this application, both with experimentation and molecular simulations. We found that the COPs of all of the IL/water systems were higher than the conventional system – LiBr/H2O. Thus, IL/water systems appear very attractive for absorption refrigeration applications.« less
Ionic Liquids as Unforeseen Assets to Fight Life-Threatening Mycotic Diseases.
Hartmann, Diego O; Petkovic, Marija; Silva Pereira, Cristina
2016-01-01
Ionic liquids discovery has celebrated 100 years. They consist solely of ions, one of which is typically organic and asymmetrical. Remarkable physical and chemical properties stirred their use as alternative solvents in many chemical processes. The recent demonstration of their occurrence in nature might boost their interest in biological sciences. In the search of mechanistic understandings of ionic liquids' ecotoxicological impacts in fungi, we have analyzed the proteome, transcriptome, and metabolome responses to this chemical stress. Data illuminated new hypotheses that altered our research path - exploit ionic liquids as tools for the discovery of pathways and metabolites that may impact fungal development and pathogenicity. As we get closer to solve the primary effects of each ionic liquid family and their specific gene targets, the vision of developing antifungal ionic liquids and/or materials, by taking advantage of elegant progresses in this field, might become a reality. Task-designed formulations may improve the performance of conventional antifungal drugs, build functional coatings for reducing allergens production, or aid in the recovery of antifungal plant polymers. The frontier research in this cross-disciplinary field may provide us unforeseen means to address the global concern of mycotic diseases. Pathogenic and opportunistic fungi are responsible for numerous infections, killing annually nearly 1.5 million immunocompromised individuals worldwide, a similar rate to malaria or tuberculosis. This perspective will review our major findings and current hypotheses, contextualizing how they might bring us closer to efficient strategies to prevent and fight mycotic diseases.
Sadeghi, Rahmat; Ebrahimi, Nosaibah
2011-11-17
A systematic study of osmotic coefficient, conductivity, volumetric and acoustic properties of solutions of ionic liquid 1-hexyl-3-methylimidazolium chloride ([C(6)mim][Cl]) in various molecular solvents has been made at different temperatures in order to study of ionic association and solvation behavior of [C(6)mim][Cl] in different solutions. Precise measurements on electrical conductances of solutions of [C(6)mim][Cl] in water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and acetonitrile at 293.15, 298.15, and 303.15 K are reported and analyzed with Barthel's low-concentration chemical model (lcCM) to obtain the limiting molar conductivities and association constants of this ionic liquid in the investigated solvents. Strong ion pairing was found for the ionic liquid in 2-propanol, 1-butanol, and 1-propanol, whereas ion association in acetonitrile, methanol and ethanol is rather weak and in water the ionic liquid is fully dissociated. In the second part of this work, the apparent molar volumes and isentropic compressibilities of [C(6)mim][Cl] in water, methanol, ethanol, acetonitrile, 1-propanol, 2-propanol, and 1-butanol are obtained at the 288.15-313.15 K temperature range at 5 K intervals at atmospheric pressure from the precise measurements of density and sound velocity. The infinite dilution apparent molar volume and isentropic compressibility values of the free ions and ion pairs of [C(6)mim][Cl] in the investigated solvents as well as the excess molar volume of the investigated solutions are determined and their variations with temperature and type of solvents are also studied. Finally, the experimental measurements of osmotic coefficient at 318.15 K for binary solutions of [C(6)mim][Cl] in water, methanol, ethanol, 2-propanol, and acetonitrile are taken using the vapor pressure osmometry (VPO) method and from which the values of the solvent activity, vapor pressure, activity coefficients, and Gibbs free energies are calculated. The results are interpreted in terms of ion association, ion-dipole interactions, and structural factors of the ionic liquid and investigated organic solvents. The ionic liquid is solvated to a different extent by the molecular solvents, and ionic association is affected significantly by ionic solvation.
Enzymatic synthesis of esculin ester in ionic liquids buffered with organic solvents.
Hu, Yifan; Guo, Zheng; Lue, Bena-Marie; Xu, Xuebing
2009-05-13
The enzymatic esterification of esculin catalyzed by Candida antarctica lipase B (Novozym 435) was carried out in ionic liquid (IL)-organic solvent mixed systems in comparison with individual systems. The reaction behaviors in IL-organic solvents were systemically evaluated using acetone as a model solvent. With organic solvents as media, the esterification rates of esculin depended mainly on its solubility in solvents; for the reactions in ILs, the reaction rates were generally low, and the anion part of the IL played a critical role in enzyme activity. Therefore, the esterification of esculin in IL-acetone mixtures made it possible to improve the solubility of esculin while the effects of ILs on lipase activity were minimized. Following the benignity of ILs to lipase activity, the anions of ILs were ranked in the order as [Tf(2)N](-) > [PF(6)](-) > [BF(4)](-) > [CF(3)SO(3)](-) > [C(4)F(9)SO(3)](-) > [TAF](-) > [MDEGSO(4)](-) > [OctSO(4)](-) > [ES](-) = [DMP](-) = [OTs](- )= Cl(-). The reaction behaviors differed in different systems and largely depended on the properties of the ILs and organic solvents. In general, improvements were observed in terms of both solubility and reaction efficiency. The knowledge acquired in this work gives a better understanding of multiple interactions in IL-organic solvent systems, which provide guidance for system design and optimization.
Sequencing proteins with transverse ionic transport in nanochannels.
Boynton, Paul; Di Ventra, Massimiliano
2016-05-03
De novo protein sequencing is essential for understanding cellular processes that govern the function of living organisms and all sequence modifications that occur after a protein has been constructed from its corresponding DNA code. By obtaining the order of the amino acids that compose a given protein one can then determine both its secondary and tertiary structures through structure prediction, which is used to create models for protein aggregation diseases such as Alzheimer's Disease. Here, we propose a new technique for de novo protein sequencing that involves translocating a polypeptide through a synthetic nanochannel and measuring the ionic current of each amino acid through an intersecting perpendicular nanochannel. We find that the distribution of ionic currents for each of the 20 proteinogenic amino acids encoded by eukaryotic genes is statistically distinct, showing this technique's potential for de novo protein sequencing.
The fish gill: site of action and model for toxic effects of environmental pollutants.
Evans, D H
1987-01-01
The gill epithelium is the site of gas exchange, ionic regulation, acid-base balance, and nitrogenous waste excretion by fishes. The last three processes are controlled by passive and active transport of various solutes across the epithelium. Various environmental pollutants (e.g., heavy metals, acid rain, and organic xenobiotics) have been found to affect the morphology of the gill epithelium. Associated with these morphological pathologies, one finds alterations in blood ionic levels, as well as gill Na,K-activated ATPase activity and ionic fluxes. Such physiological disturbances may underly the toxicities of these pollutants. In addition, the epithelial transport steps which are affected in the fish gill model resemble those described in the human gut and kidney, sites of action of a variety of environmental toxins. Images FIGURE 1. a FIGURE 1. b FIGURE 3. PMID:3297663
Quecholac-Piña, Xochitl; García-Rivera, Mariel Anel; Espinosa-Valdemar, Rosa María; Vázquez-Morillas, Alethia; Beltrán-Villavicencio, Margarita; Cisneros-Ramos, Adriana de la Luz
2017-11-01
Plastics are widely used in the production of short-life products, which are discarded producing an accumulation of these materials and problems due to their persistence in the environment and waste management systems. Degradable plastics (compostable, oxodegradable) have been presented as an alternative to decrease the negative effect of plastic waste. In this research, the feasibility of degrading a commercially available compostable film and oxodegradable polyethylene, with and without previous abiotic oxidation, is assessed in a home composting system. Reactors (200 L) were used to degrade the plastic films along with a mixture of organic food waste (50 %), mulch (25 %), and dry leaves (25 %), amended with yeast and a solution of brown sugar to increase the speed of the process. The presence of the plastic film did not affect the composting process, which showed an initial increase in temperature and typical profiles for moisture content, pH, with a final C/N of 17.4. After 57 days, the compostable plastic has decreased its mechanical properties in more than 90 %, while the oxodegradable film did not show significant degradation if it was not previously degraded by UV radiation. The use of these plastics should be assessed against the prevailing waste management system in each city or country. In the case of Mexico, which lacks the infrastructure for industrial composting, home composting could be an option to degrade compostable plastics along organic waste. However, more testing is needed in order to set the optimal parameters of the process.
Code of Federal Regulations, 2011 CFR
2011-07-01
...; organic chemicals; plastics and resins manufacturing; pulp and paper industry; rubber and miscellaneous plastic products; stone, glass, clay, and concrete products; textile manufacturing; transportation..., water supply treatment plant, or air pollution control facility, exclusive of the treated effluent from...
Research highlights: impacts of microplastics on plankton.
Lin, Vivian S
2016-02-01
Each year, millions of metric tons of the plastic produced for food packaging, personal care products, fishing gear, and other human activities end up in lakes, rivers, and the ocean. The breakdown of these primary plastics in the environment results in microplastics, small fragments of plastic typically less than 1-5 mm in size. These synthetic particles have been detected in all of the world's oceans and also in many freshwater systems, accumulating in sediment, on shorelines, suspended in surface waters, and being ingested by plankton, fish, birds, and marine mammals. While the occurrence of plastics in surface waters has been surveyed in a number of studies, the impacts of microplastics on marine organisms are still being elucidated. This highlight features three recent publications that explore the interactions of microplastics with planktonic organisms to clarify the effects of these pollutants on some of the ocean's smallest and most important inhabitants.
Deformation behavior of human dentin in liquid nitrogen: a diametral compression test.
Zaytsev, Dmitry; Panfilov, Peter
2014-09-01
Contribution of the collagen fibers into the plasticity of human dentin is considered. Mechanical testing of dentin at low temperature allows excluding the plastic response of its organic matrix. Therefore, deformation and fracture behavior of the dentin samples under diametral compression at room temperature and liquid nitrogen temperature are compared. At 77K dentin behaves like almost brittle material: it is deformed exclusively in the elastic regime and it fails due to growth of the sole crack. On the contrary, dentin demonstrates the ductile response at 300K. There are both elastic and plastic contributions in the deformation of dentin samples. Multiple cracking and crack tip blunting precede the failure of samples. Organic phase plays an important role in fracture of dentin: plasticity of the collagen fibers could inhibit the crack growth. Copyright © 2014 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Zhorin, V. A.; Kiselev, M. R.; Roldugin, V. I.
2017-11-01
DSC is used to measure the thermal effects of processes in mixtures of solid organic dibasic acids with powdered aluminum, subjected to plastic deformation under pressures in the range of 0.5-4.0 GPa using an anvil-type high-pressure setup. Analysis of thermograms obtained for the samples after plastic deformation suggests a correlation between the exothermal peaks observed around the temperatures of degradation of the acids and the thermally induced chemical reactions between products of acid degradation and freshly formed surfaces of aluminum particles. The release of heat in the mixtures begins at 30-40°C. The thermal effects in the mixtures of different acids change according to the order of acid reactivity in solutions. The extreme baric dependences of enthalpies of thermal effects are associated with the rearrangement of the electron subsystem of aluminum upon plastic deformation at high pressures.
Obadia, Mona M; Mudraboyina, Bhanu P; Serghei, Anatoli; Montarnal, Damien; Drockenmuller, Eric
2015-05-13
Exploiting exchangeable covalent bonds as dynamic cross-links recently afforded a new class of polymer materials coined as vitrimers. These permanent networks are insoluble and infusible, but the network topology can be reshuffled at high temperatures, thus enabling glasslike plastic deformation and reprocessing without depolymerization. We disclose herein the development of functional and high-value ion-conducting vitrimers that take inspiration from poly(ionic liquid)s. Tunable networks with high ionic content are obtained by the solvent- and catalyst-free polyaddition of an α-azide-ω-alkyne monomer and simultaneous alkylation of the resulting poly(1,2,3-triazole)s with a series of difunctional cross-linking agents. Temperature-induced transalkylation exchanges of C-N bonds between 1,2,3-triazolium cross-links and halide-functionalized dangling chains enable recycling and reprocessing of these highly cross-linked permanent networks. They can also be recycled by depolymerization with specific solvents able to displace the transalkylation equilibrium, and they display a great potential for applications that require solid electrolytes with excellent mechanical performances and facile processing such as supercapacitors, batteries, fuel cells, and separation membranes.
Current research trends on plastic pollution and ecological impacts on the soil ecosystem: A review.
Chae, Yooeun; An, Youn-Joo
2018-05-09
Plastic pollution in the environment is currently receiving worldwide attention. Improper dumping of disused or abandoned plastic wastes leads to contamination of the environment. In particular, the disposal of municipal wastewater effluent, sewage sludge landfill, and plastic mulch from agricultural activities is a serious issue and of major concern regarding soil pollution. Compared to plastic pollution in the marine and freshwater ecosystems, that in the soil ecosystem has been relatively neglected. In this study, we discussed plastic pollution in the soil environment and investigated research on the effects of plastic wastes, especially microplastics, on the soil ecosystem. We found that earthworms have been predominantly used as the test species in investigating the effects of soil plastic pollution on organisms. Therefore, further research investigating the effects of plastic on other species models (invertebrates, plants, microorganisms, and insects) are required to understand the effects of plastic pollution on the overall soil ecosystem. In addition, we suggest other perspectives for future studies on plastic pollution and soil ecotoxicity of plastics wastes, providing a direction for such research. Copyright © 2018 Elsevier Ltd. All rights reserved.
Luo, Hewei; Yu, Chenmin; Liu, Zitong; Zhang, Guanxin; Geng, Hua; Yi, Yuanping; Broch, Katharina; Hu, Yuanyuan; Sadhanala, Aditya; Jiang, Lang; Qi, Penglin; Cai, Zhengxu; Sirringhaus, Henning; Zhang, Deqing
2016-01-01
Organic semiconductors with high charge carrier mobilities are crucial for flexible electronic applications. Apart from designing new conjugated frameworks, different strategies have been explored to increase charge carrier mobilities. We report a new and simple approach to enhancing the charge carrier mobility of DPP-thieno[3,2-b]thiophene–conjugated polymer by incorporating an ionic additive, tetramethylammonium iodide, without extra treatments into the polymer. The resulting thin films exhibit a very high hole mobility, which is higher by a factor of 24 than that of thin films without the ionic additive under the same conditions. On the basis of spectroscopic grazing incidence wide-angle x-ray scattering and atomic force microscopy studies as well as theoretical calculations, the remarkable enhancement of charge mobility upon addition of tetramethylammonium iodide is attributed primarily to an inhibition of the torsion of the alkyl side chains by the presence of the ionic species, facilitating a more ordered lamellar packing of the alkyl side chains and interchain π-π interactions. PMID:27386541