Salt effects on the conformation of a ‘statistical’ copolymer of l-leucine and l-lysine

For studying the influence of water structure breaking and making anions on the conformation of poly(α-amino acids) containing hydrophobic and ionic side chains, c.d. measurements on ‘statistical copolymers of l-leucine and l-lysine were carried out in LiClO₄, NaClO₄, Li₂SO₄, Na₂SO₄, KF, NaF, and NaCl solutions and also in salt-free water. Copolymers with 50 mol% l-leucine do not form α-helices in pure water at pH 7 (20°C); however LiClO₄ and NaClO₄ at concentrations as low as 0.003 moll^?1 induce α-helix formation almost independent of cation. Surprisingly, not only ClO^?₄ but also SO^2?₄ has an α-helix inducing effect in this case, in contrast with basic homopoly (α-amino acids), where such an effect of SO^2?₄ was not observed. Therefore the presence of l-leucyl residues seems to be responsible for this α-helix inducing effect of sulphate anions. This agrees with the fact that sulphate stabilizes the ordered periodic conformation of native proteins as the increase of denaturing temperature shows. It can be assumed that the results of these measurements support the assumptions on the influence of water structure in making SO₄ anions on hydrophobic interactions, as well as of water structure breaking ClO₄ anions.     

Adsorption of perchlorate onto raw and oxidized carbon nanotubes in aqueous solution

Perchlorate (ClO₄^?) is an emerging trace contaminant. The adsorption of ClO₄^? on raw and oxidized carbon nanotubes (CNTs) was investigated to elucidate the affinity mechanism of CNTs with anion pollutants. The adsorption of ClO₄^? into different CNTs increased in the order multi-walled CNTs < single-walled CNTs < double-walled CNTs (DWCNTs). Co-existing anions (SO₄^2?, NO₃^?, Cl^?) significantly weakened ClO₄^? adsorption, while the co-existence of Fe³⁺ and cetyltrimethylammonium cations increased ClO₄^? adsorption 2- to 3-fold. ClO₄^? adsorption was promoted by oxidized DWCNTs due to the introduction of more oxygen-containing functional groups, which served as additional adsorption sites. The pH values significantly affected the zeta potential of raw and oxidized DWCNTs and thus ClO₄^? adsorption. The pH-dependent curves of ClO₄^? adsorption on CNTs were distinct from those of conventional sorbents (e.g., activated carbon and resin). Maximum ClO₄^? adsorption occurred at pH = the isoelectric point (pH_IEP) + 0.85 rather than at pH < pH_IEP, which cannot be explained by electrostatic interactions alone. Hydrogen bonding is proposed to be a dominant mechanism at neutral pH for the interaction of ClO₄^? with CNTs, and variations of ClO₄^? affinity with CNTs in different pH ranges are illustrated.     

Can Kosmotropic Salt/Chaotropic Ionic Liquid (Salt/Salt Aqueous Biphasic Systems) be Used to Remove Pertechnetate From Complex Salt Waste?

Abstract

Aqueous solutions of water‐structuring, kosmotropic salts (e.g., salts of PO₄ ^3?, HPO₄ ^2?, CO₃ ^2?) will salt‐out water‐destructuring chaotropic ionic liquids (ILs) (e.g., 1‐butyl‐3‐methylimidazolium chloride, ([C₄mim]Cl)) forming salt/salt aqueous biphasic systems (ABS). The chaotropic pertechnetate (TcO₄ ^?) anion will partition without the use of an extractant into the IL‐rich phase. These complex salt/salt ABS are not unlike the complex and salt‐rich Hanford tank waste, and thus have been used here as a simple model to show effectiveness in the partitioning of TcO₄ ^? from such tank waste into an IL‐rich phase.     

Thermal Properties of Macrocyclic Polyethers: Implications for the Design of Crown Ether-Based Ionic Liquids

The most commonly studied classes of ionic liquids (ILs) comprise relatively large and asymmetric heterocyclic cations (e.g., diakylimidazolium or N-alkylpyridinium) in combination with any of a wide variety of inorganic (e.g., BF₄^?, Cl^?) or organic (e.g., bis[(trifluoromethyl- sulfonyl)imide], Tf₂N^?) anions. Recently it has been shown that ILs can also be formed by complexation reactions of metal cations (e.g., Li⁺, as its Tf₂N^? salt) with various neutral ligands (e.g., cyclohexano-15-crown-5 or alkylamines). Because the upper limit of the useful temperature range of any IL is governed by its thermal stability, and because the thermal stability of a neutral ligand (i.e., its propensity to either volatilize or decompose) is of obvious importance in determining that of an IL prepared from it, a systematic examination of the thermal properties of a series of macrocyclic polyethers of potential utility in the synthesis of new ILs has been undertaken. The results show that the temperature corresponding to the onset of mass loss upon heating (i.e., evaporation and/or decomposition) varies with the ring size, substitution, nature of the donor atoms, and stereochemistry of the macrocycle, but is most strongly influenced by the molecular weight and aromatic content of the compound.     

Aerosol Acidity Measurement Using Colorimetry Coupled With a Reflectance UV-Visible Spectrometer

In this study, aerosol acidity was measured using colorimetry integrated with a Reflectance UV-Visible spectrometer (C-RUV). An inorganic aerosol comprising NH₄ ⁺?H⁺?SO₄ ^2??H₂O was generated using an atomizer and introduced into a 2-m³ indoor Teflon film chamber. The produced aerosol was collected on the Teflon-coated glass fiber filter dyed with metanil yellow (MY) as an indicator for measuring proton concentrations in aerosol. A calibration curve for measuring aerosol acidity using the C-RUV technique was obtained through the relationship between the absorbance of the UV-Visible spectrum of the filter sample vs. theoretically calculated proton concentrations using the E-AIM Model II. To develop the C-RUV method under various humidities, the aerosol filter sample was mounted inside a small optical flow chamber controlled for humidity in situ. The humidity effect on the equilibrium thermodynamics of the indicator was theoretically described by inclusion of excess acidity (X) into the calibration curve. The calibration curve obtained from relatively highly acidic aerosols (e.g., H₂SO₄, NH₄H₃(SO₄)₂, and (NH₄)₇H₁₃(SO₄)₁₀) was extrapolated to estimate proton concentrations for weakly acidic aerosols (e.g., NH₄HSO₄ and (NH₄)₃H(SO₄)₂), which is more relevant to the ambient aerosol acidity but has been poorly predicted with typical inorganic thermodynamic models due to the limited experimental data. The C-RUV technique of this study permits one to estimate aerosol acidity for a variety of compositions of the NH₄ ⁺?H⁺?SO₄ ^2??H₂O system including both ammonia-poor and ammonia-rich sulfate aerosols.

Copyright 2012 American Association for Aerosol Research     

EXTRACTION OF INDIUM( III) FROM BROMIDE AND THIOCYANATE MEDIA WITH 1-PHENYL-3-HETHYL-1-BENZOYLPYRAZOL-5-ONE; EFFECT OF LIPOPHILIC AMMONIUM SALTS

1-phenyl-3-methyl-4-benzoylpyrazol-5-one (HL) in toluene extracts In(III) from ClO₄ ^?, (Br^?, CIO ClO₄ ^?, ) and Br^? media according to the extraction equilibria (1) and (2). Tri-n-octylmethylammonium bromide (B⁺Br^?) induces a medium synergic effect for Br^? and (Br^?,NO₃ ^?) media, which is cancelled in ClO₄ ^?medium. It corresponds to the extraction of (B⁺InBr_xL_4-x) ion pairs. On the contrary, from SCN^? or (SCN^?,ClO₄ ^?) media, In is extracted by HL according to only (1) and no synergism is obtained with tri-n-octylammonium salt.

These results are compared with those obtained with Cl^? and (C1^?,ClO₄ ^?) aqueous media. They are to a great extent explained by taking into account the complexing of In³⁺ by aqueous inorganic anions, the lipophilicity of the diverse species and the anionic exchanges in the B⁺X^? ion pairs.     

Improved performance of the direct methanol redox fuel cell

Advancements in the performance of the direct methanol redox fuel cell (DMRFC) were made through anolyte/catholyte composition and cell temperature studies. Catholytes prepared with different iron salts were considered for use in the DMRFC in order to improve the catholyte charge density (i.e., iron salt solubility) and fuel cell performance. Following an initial screening of different iron salts, catholytes prepared with FeNH₄(SO₄)₂, Fe(ClO₄)₃ or Fe(NO₃)₃ were selected and evaluated using electrolyte conductivity measurements, cyclic voltammetry and fuel cell testing. Solubility limits at 25 °C were observed to be much higher for the Fe(ClO₄)₃ (>2.5 M) and Fe(NO₃)₃ (>3 M) salts than FeNH₄(SO₄)₂ (~1 M). The Fe(ClO₄)₃ catholyte was identified as a suitable candidate due to its high electrochemical activity, electrochemical reversibility, observed half-cell potential (0.83 V vs. SHE at 90 °C) and solubility. DMRFC testing at 90 °C demonstrated a substantial improvement in the non-optimized power density for the perchlorate system (79 mW cm⁻²) relative to that obtained for the sulfate system (25 mW cm⁻²). Separate fuel cell tests showed that increasing the cell temperature to 90 °C and increasing the methanol concentration in the anolyte to 16.7 M (i.e., equimolar H₂O/CH₃OH) yield significant DMRFC performance improvements. Stable DMRFC performance was demonstrated in short-term durability tests.     

N-bromo-poly(styrene-co-divinylbenzene) sulphonamide metal salts. Synthesis and basic properties

Macromolecular pendant group N-monobromosulphonamide metal salts ? SO₂NBr^?M⁺ having a macroporous styrene-divinylbenzene matrix structure have been obtained by two methods: (a) by the action of aqueous metal hypobromites on the appropriate macromolecular pendant group sulphonamide, and (b) by the action of an aqueous metal bromide on the appropriate macromolecular N-chlorosulphonamide metal salt. In each case the sodium salt product was obtained with a 100% functional yield and it contained 2.1 mmol.g^?1 ? SO₂NBr^?Na⁺ groups, i. e., 4.2 meq · g^?1 of active bromine. The stability of the resin was investigated in the range 20–100°C in the dry state as well as in aqueous media. A thermoanalysis (TG, DTG, and DTA curves) was carried out up to 1000°C and its course was interpreted. The resin has brominating, oxidative, microbiocidic, and ionexchanging properties. It reacts in a reversible way: after the loss of the active bromine, it can be reactivated again.     

Solid-liquid equilibria in concentrated aqueous salt solutions—systems with a common ion

A thermodynamic correlation is presented for solid-liquid equilibria in concentrated aqueous salt systems containing a common ion. It is assumed that no solid solutions are formed, although the solid phase can be a pure salt, a multiple salt or a hydrate. Predictions of solid-liquid equilibria in multicomponent systems are made using parameters calculated from solid-liquid equilibrium data for the constituent binary and ternary systems.Parameters are given for the prediction of solid-liquid equilibria in the aqueous system containing Na⁺, K⁺, Mg⁺⁺, NO^?₃, Cl^?, SO^--₄ from 0–50°C. These parameters correlate the available solid-liquid equilibrium data for ternary systems with an error in liquid-phase composition of less than 2 grams salt/100 grams H₂O. Errors are similar in the estimation of solid-liquid equilibria in four-component systems such as NaNO₃-NaC1-Na₂SO₄-H₂O.     

A new insight into the mechanism of influence of different inorganic salts on optical properties of water‐soluble cationic conjugated polymers

The water‐soluble conjugated polyelectrolyte poly{2,5‐bis[3‐(N,N,N‐triethylammoniumbromide)‐1‐oxapropyl]‐1,4‐phenylenevinylene} (P2) was synthesized and the influences of different inorganic salts on the optical properties of the polyelectrolyte were studied. New absorption and emission peaks at longer wavelength can be observed in the case of P2 with addition of different concentrations of Cl^? or NO₃^?, whereas addition of I^? or ClO₄^? only induces a red shift. Interestingly, addition of SO₄^2? or F^? does not result in considerable changes in optical spectra. Through UV‐visible spectrometry, photoluminescence, ¹H NMR and cyclic voltammetry, we showed that the nature of the inorganic salts brings these different changes. The special structure of the bond of NO₃^? and the large electronegativity of chlorine lead to an electron transfer between the conjugated polymer and the negative ions. The large radius of I^? and the weak electron withdrawing ability of ClO₄^? only bring a red shift of optical spectra. In addition, SO₄^2? and F^? do not affect the spectra significantly, except that the fluorescence intensity falls slightly indicating that P2 is not sensitive to these ions. Copyright © 2011 Society of Chemical Industry     

Pitting of zinc in leclanche and related electrolytesII. Mode of growth of pits and rate of propagation

The nucleation and growth of pits on battery zinc alloy electrodes in commercial (standard) Leclanché and related electrolytes has been studied quantitatively using both potentiodynamic and potentiostatic techniques. Pit numbers, volumes, surface areas and distributions have been determined by optical microscopy. The effect on pitting kinetics of pH, NH⁺₄ ions and various anions: Br^?, Cl^?, ClO^?₄ and SO^2?₄, has also been investigated. A theory is provided which acts as a basis for interpreting the observed time dependence of the pitting current density at constant potential and deviations of the real system from the idealized model are discussed.     

Exceptional ion-exchange selectivity for perchlorate based on polyaniline films

Polyaniline (PANI) films were electrochemically synthesized on graphite electrode and their ion-exchange selectivities for ClO₄⁻ were investigated. Cyclic voltammetry (CV) results showed that PANI-H₂SO₄ film represented higher selectivity for ClO₄⁻ than PANI–HCl and PANI–HClO₄. Furthermore, the CV records of PANI–H₂SO₄ film in different acidic solutions demonstrated that ClO₄⁻ exchange was performed in a lower potential range (from −0.025 V to 0.097 V), which is distinguished from SO₄²⁻ and Cl⁻. Additionally, chronoamperomertry (CA) studies of PANI–H₂SO₄ film in 0.1 M various acidic solutions (H₂SO₄, HCl and HClO₄) confirmed that the diffusion coefficient values in HClO₄ (13.319/18.184 × 10⁻⁶ cm² s⁻¹) were the biggest during doping/de-doping process. The exceptional ion-exchange selectivity for ClO₄⁻ was explained by the process of dominant accumulation, quick insertion of anions, and the sluggish mobility of ClO₄⁻ inside the membrane. Results of present work demonstrated that PANI may serve as a promising membrane for ClO₄⁻ removal by ion-exchange process.     

Polyaniline salt containing dual dopants,pyrelenediimide tetracarboxylic acid,and sulfuric acid: Fluorescence and supercapacitor

Storage of energy is considered as the most germane technologies to address the future sustainability. In this study, aniline was chemically oxidized with a controlled concentration of pyrelenediimide tetracarboxylic acid (PDITCA) by ammonium persulfate to polyaniline salt (PANI‐H₂SO₄‐PDITCA), with nanorods morphologies, having a sensibly decent conductivity of 0.8 S cm^?1, wherein H₂SO₄ was generated from ammonium persulfate during polymerization. PANI‐H₂SO₄‐PDITCA salt showed bathochromic fluorescence shift (595 nm) compared to PDITCA (546 nm). The Brunauer–Emmett–Teller surface area of the PANI‐H₂SO₄‐PDITCA‐25 and PANI‐H₂SO₄‐PDITCA‐50 were 18.3 and 21.4 m² g^?1, respectively. Furthermore, its energy storage efficiency was evaluated by supercapacitor cell configuration. The composite PANI‐H₂SO₄‐PDITCA‐50 showed capacitance 460 F g^?1 at 0.3 A g^?1 and large cycle life 85,000 cycles with less retention of 77% to its original capacitance (200 F g^?1) even at a better discharge rate of 3.3 A g^?1. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45456.     

EFFECT OF ANIONS ON THERMODYNAMICS OF EXTRACTION OF Am(III) AND Eu(III) WITH OCTYL(PHENYL)-N,N-DIISOBUTYL-CARBAMOYLMETHYLPHOSPHINE OXIDE

The extraction of Am(III) and Eu(III) by octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) in xylene from aqueous media containing 1.0 M NH₄NO₃, NH₄SCN, NH₄ClO₄ or a mixture of 0.3 M NH₄NO₃ + 0.7 M NH₄ClO₄ at pH 2.70 and at the temperatures of 15, 25, 35 and 45±0.1 °C has been studied. At all the temperatures, the species extracted were ML₃ · 3CMPO (M = Am(III) or Eu(III), L = NO₃ ^?, SCN^? or ClO₄ ^?) and M(NO₃)(ClO₄)₂ · 3CMPO. The thermodynamic parameters of the extraction reactions have been evaluated using the temperature coefficient method. The ?ΔG values follow the order SCN^? > NO₃ ^? + ClO₄ ^? > NO₃ ^? ≈ ClO₄ ^?, whereas the ?ΔH values an order NO₃ ^? + ClO₄ ^? > SCN^? > NO₃ ^? ≈ ClO₄ ^?. The effect of these anions on the thermodynamic parameters have been discussed employing compensation effects and also on the basis of the energy associated with the transfer of these anions from aqueous to the extractant phase.     

Preparation and Characterization of Energetic Nanocomposites of Organic Gel – Inorganic Oxidizers

Two types of polymeric sols, resorcinol‐formaldehyde (RF) and resorcinol‐furfural (RFur), were mixed in a water‐containing medium with aqueous solutions of inorganic salts: NH₄ClO₄, Mg(ClO₄)₂, and NH₄NO₃. After gelation and an ambient pressure drying, hybrid nanocomposites with properties of energetic materials were obtained. It was stated that salt concentration and addition of a second solvent (e.g., methanol or N,N‐dimethylformamide) to the mixture of reagents have crucial meaning for gel formation. In the case when only water was used, the mixture of organic sol/inorganic salt did not transfer from sol to gel, and precipitates were formed. Conventional drying of wet gelled composites leads to rigid material called xerogels. The RF xerogels are red and RFur xerogels are black. Typically, xerogels are transparent at low salt concentration (below 30%). The microstructure, morphology, and some other properties of chosen composites were studied by means of HR SEM, AFM, XRD, DTA/TG, and N₂ adsorption isotherm techniques. SEM observation revealed that sizes of the oxidizer particles vary from less than 100 nm to ca. 1000 nm. XRD analyses also confirmed the presence of nanometer‐sized crystals of oxidizers in some formulations. The specific surface area of polymeric matrix/oxidizer composites was found to be in the range from 0.002 to 0.3 m² g⁻¹. After removing the salt from the composites (by extraction with boiling water), the specific surface area grows even up to 210 m² g⁻¹. TG/DTA analyses showed that the tested composites decompose as typical energetic materials. If pre‐heated and exposed to flame, some of them (especially RF/Mg(ClO₄)₂ composites) undergo violent deflagration with loud sound and flash effect.     

Effects of dopants and copolymerization on Schottky barriers of polypyrrole and polyindole/metal interfaces

Schottky-barrier diode devices were fabricated in a sandwich configuration with poly(pyrrole-co-indole) copolymer semiconducting films prepared by electropolymerization. Effect of different dopants of ClO₄ ^?, BF₄ ^?, C₇H₇SO₃ ^? and [Fe(CN)₆]^3? on the electronic properties of the fabricated devices was followed using Ag, In, Al and Cu metal junctions. Current?Cvoltage and capacitance?Cvoltage characteristics were recorded for making a comparative evaluation of the electronic and junction properties of the devices. The electrical characteristics of the junctions were analyzed based on the standard thermionic emission theory. Polymer doped by ClO₄ ^? showed lower reverse saturation currents and ideality factor but higher potential barriers and rectification ratios. Effect of dopant ions and copolymerization on the optical band gaps (E _g) of the films were investigated and the optical transmissions of the doped copolymer films were measured in the wavelength range of 250?C900?nm. It was shown that the energy gap of copolymers laid between those of corresponding homopolymers and polyindole (PIN) doped by [Fe(CN₆)]^?3 had E _g less than that of polymer doped by other anions whereas E _g of polypyrrole was independent of dopant ions. Also, the morphology of the polymeric films revealed the surface of the PIN doped with ClO₄ ^? was very smooth which created a good contact with indium metal.     

Anionic polymerization of ethylene oxide with cryptates as counterions: 2

A kinetic study of the anionic polymerization of ethylene oxide has been made in tetrahydrofuran at 20°C, with the cryptate Cs⁺ + [TC] as counterion, [TC] being a spheroidal macrotricyclic ligand. Conductance measurements have been made on THF solutions of ?₄BCs + [TC]. Ionic associations higher than cryptated ion pairs are negligible for living end concentrations lower than 3 × 10^?4 moll^?1. k_± and the alkoxide ion pair dissociation constant K_D were determined from both sets of kinetic data obtained with and without added salt knowing the value of k_? from kinetic data performed with K⁺ + [222] as counterion. Free alkoxide ions are about twenty times more reactive than cryptated caesium ion pairs.     

A novel double-stranded dinuclear copper(I) helicate having a photoluminescent CuI2N8 chromophore

Bis-(pyridinal)-ethylenediimine (L) affords [Cu^I₂L₂]X₂ (X=ClO₄⁻ and PF₆⁻). The X-ray crystal structure of the ClO₄⁻ salt shows that the cation [Cu^I₂L₂]²⁺ is a double-stranded helicate. The PF₆⁻ salt exhibits a single emission band (maxima, 540 nm) in solution at room temperature (quantum yield: 2×10⁻⁵ in methanol, 1×10⁻⁵ in CH₂Cl₂).     

PRECIPITATION CONDITIONS OF CHEVREUL'S SALT FROM SYNTHETIC AQUEOUS CuSO4 SOLUTIONS

In this study, synthetic aqueous CuSO₄ solution was prepared at various concentrations. Chevreul's salt was precipitated by passing SO₂ through these solutions. Chevreul's salt, a mixed valence copper sulfite, Cu₂SO₃·CuSO₃·2H₂O, was characterized by XRD and SEM. The effects of parameters such as initial solution concentration, SO₂ feeding rate, reaction time, and initial solution pH on precipitation of Chevreul's salt were investigated. 2ⁿ factorial experimental design and orthogonal central composite design methods in the precipitation experiments were used. It was observed that the effective parameters on the precipitation of Chevreul's salt were initial solution concentration, SO₂ feeding rate, and initial solution pH. The optimum conditions obtained for maximum copper precipitation were: initial solution concentration 1.14 M, SO₂ feeding rate 329.35 L.h.^?1, reaction time 25 min, and initial solution pH 8.5. Constant parameters chosen at the initial stage of the reaction were: temperature 62°C, stirring speed 600 rpm, and reaction pH 3 (Çalban et al., 2006). Under these optimum conditions, the percentage of precipitated copper from synthetic aqueous CuSO₄ solutions was 99.95.     

Anion-induced conformational transition of poly(l-arginine) and its two homologues

The interaction of various anions with poly(l-arginine) and its two homologues, poly(l-homoarginine) and poly(l-α-amino-γ-guanidinobutyric acid), has been studied in the neutral pH region. These polypeptides were found to change their conformations from coil to helix due to I^?, ClO^?₄ and SCN^?, and among them poly(l-homoarginine) and poly(l-arginine) were found to change conformation at smaller concentrations of the anions than poly(l-lysine). The helix of poly(l-homoarginine) was induced in the lyotropic series of the counteranions. Using the van't Hoff enthalpies for the transition of the polypeptides and the transition enthalpies obtained from calorimetry, the various thermodynamic parameters of the transitions were calculated by use of a theory based on the non-specific and the specific binding interactions of the anions with the charged sites on the polypeptides. The binding constants of ClO^?₄ and SCN^? with poly(l-homoarginine) and poly(l-arginine) were found to be four times as large as those with poly(l-lysine). The free energy changes of the transitions from coil to helix of poly(l-homoarginine) and poly(l-arginine) were found to be more negative than that of poly(l-lysine). From these results, the guanidinium ion can be concluded to form easily the ion pair with the anions on the polymer surface, thus allowing poly(l-homoarginine) and poly(l-arginine) to change their conformations at smaller concentrations of the anions than poly(l-lysine).