Nature Of Counterion Research Articles

Antibacterial activities of mono-, di- and tri-substituted triphenylamine-based phosphonium ionic liquids

We report the synthesis of new mono, di and tri phosphonium ionic liquids and the evaluation of their antibacterial activities on both Gram-positive and Gram-negative bacteria from the ESKAPE-group. Among the molecules synthesized some of them reveal a strong bactericidal activity (MIC = 0.5 mg/L) for Gram-positive bacteria (including resistant strains) comparable to that of standard antibiotics. A comparative Gram positive and Gram negative antibacterial activities shows that the nature of counter-ion has no significant effects. Interestingly, the increase of phosphonium lateral chains (from 4 to 8 carbons) results in a decrease of antibacterial activities. However, the increase of the spacer length has a positive influence on the activity on both Gram-positive and Gram-negative bacteria except for E. aerogenes. Finally, the increased charge density has no effect on the Gram-positive antibacterial activities (MIC between 2 and 4 mg/L) but seems to attenuate (except for P. aeruginosa) the discrimination between Gram-positive and Gram-negative. Overall these results suggest a unique mechanism of action of these triphenylamine-phosphonium ionic liquid derivatives.

Influence of the Electropolymerization Parameters on the Doping Level of Polybithiophene Films Grown in Acetonitrile and Water

Electropolymerized polythiophene (PTh) is a conductive polymer with low crystallinity, excellent thermal stability, and good conductivity. Its applications strongly depend on the electrochemical conditions employed during film growth, the nature of the doping counterion, the substituents attached to the thiophene ring, and the reaction medium employed. Electropolymerization of bithiophene (BTh) to produce polybithiophene (PBTh) can be successful both in aqueous and organic media. The objective of the present study was to compare the influence of the electropolymerization conditions on the doping level (δ) of PBTh films. A high doping level was reached using ACN as solvent (% δ = 25.58% ± 0.77), while in water the electropolymerization was strongly inhibited. The study of in-situ conductance during electropolymerization in ACN showed a conductance increase with the number of cycles, while conductance did not increase in water. This electropolymerization inhibition is attributed to a nucleophilic attack by the H2O molecule on the cationic species formed during the oxidation of PBTh.

Isothiourea-Catalyzed Enantioselective Addition of 4-Nitrophenyl Esters to Iminium Ions

Isothioureas catalyze the enantioselective addition of 4-nitrophenyl esters to tetrahydroisoquinoline-derived iminium ions. 4-Nitrophenoxide, generated in situ from initial N-acylation of the isothiourea by the 4-nitrophenyl ester, is used to facilitate catalyst turnover in this reaction process. Optimization showed that 4-nitrophenyl esters give the best reactivity in this protocol over a range of alternative aryl esters, with the observed enantioselectivity markedly dependent on the nature of the iminium counterion. Highest yields and enantioselectivity were obtained using iminium bromide ions generated in situ via photoredox catalysis using BrCCl3 and Ru(bpy)3Cl2 (0.5 mol %) and commercially available tetramisole (5 mol %) as the Lewis base catalyst. The scope and limitations of this procedure was developed, giving the desired β-amino amide products in up to 96% yield, 79:21 diastereomeric ratio (dr), and ermajor (2R,1′S) 99.5:0.5.

The influence of the ionic strength of the medium and the nature of counterions on the interaction of DNA molecule with derivatives of actinocin and isoquinoline

The influence of the ionic strength of the medium and the nature of counterions on the interaction of DNA molecule with derivatives of actinocin and isoquinoline

Interaction of testosterone-based compounds with dodecyl sulphate monolayers at the air-water interface.

A series of atomistic molecular dynamics simulations were performed for investigating the interactions between three different testosterone-based compounds (testosterone (T), testosterone propionate (TP) and testosterone enanthate (TE)) and sodium dodecyl sulphate (SDS) and ammonium dodecyl sulphate (ADS) monolayers, which vary only in the sodium or ammonium counterions used to neutralise the sulphate headgroup. These simulations were used to investigate how the structural and interfacial properties of the monolayer were affected by changing the number of drug molecules present per monolayer, and the chemical nature of the surfactant counterions and the testosterone-based compounds. Our results show that the structure of the interfacial water layer is affected by the change of the counterion but not the chemistry of the drug molecules. As a result of the difference in their chemical structure, the T, TP and TE drug molecules prefer different locations and orientations within the monolayers. Finally, we observed that the hydration of the drug molecules encapsulated within the ADS monolayers is significantly less than when they are encapsulated within the SDS monolayers. Understanding the role that the counterion and the chemistry of the drug molecules play in these systems provides us with a detailed description of the interactions that cause ADS micelles to encapsulate significantly less drug molecules than SDS micelles, which we have recently observed experimentally.

Alkali metal ion exchanged ZSM-5 catalysts: on acidity and methanol-to-olefin performance

The acid site density and counter ion nature impact the proportion of alkene- and aromatic-based MTO reaction cycles.

Ionic Conductivity and Assembled Structures of Imidazolium Salt-Based Block Copolymers with Thermoresponsive Segments.

Ionic liquid-based block copolymers composed of ionic (solubility tunable)–nonionic (water-soluble and thermoresponsive) segments were synthesized to explore the relationship between ionic conductivity and assembled structures. Three block copolymers, comprising poly(N-vinylimidazolium bromide) (poly(NVI-Br)) as a hydrophilic poly(ionic liquid) segment and thermoresponsive poly(N-isopropylacrylamide) (poly(NIPAM)), having different compositions, were initially prepared by RAFT polymerization. The anion-exchange reaction of the poly(NVI-Br) in the block copolymers with lithium bis(trifluoromethanesulfonyl)imide (LiNTf2) proceeded selectively to afford amphiphilic block copolymers composed of hydrophobic poly(NVI-NTf2) and hydrophilic poly(NIPAM). Resulting poly(NVI-NTf2)-b-poly(NIPAM) exhibited ionic conductivities greater than 10−3 S/cm at 90 °C and 10−4 S/cm at 25 °C, which can be tuned by the comonomer composition and addition of a molten salt. Temperature-dependent ionic conductivity and assembled structures of these block copolymers were investigated, in terms of the comonomer composition, nature of counter anion and sample preparation procedure.

New Pyrazole-Hydrazone Derivatives: X-ray Analysis, Molecular Structure Investigation via Density Functional Theory (DFT) and Their High In-Situ Catecholase Activity.

The development of low-cost catalytic systems that mimic the activity of tyrosinase enzymes (Catechol oxidase) is of great promise for future biochemistry technologic demands. Herein, we report the synthesis of new biomolecules systems based on hydrazone derivatives containing a pyrazole moiety (L1–L6) with superior catecholase activity. Crystal structures of L1 and L2 biomolecules were determined by X-ray single crystal diffraction (XRD). Optimized geometrical parameters were calculated by density functional theory (DFT) at B3LYP/6–31G (d, p) level and were found to be in good agreement with single crystal XRD data. Copper (II) complexes of the compounds (L1–L6), generated in-situ, were investigated for their catalytic activities towards the oxidation reaction of catechol to ortho-quinone with the atmospheric dioxygen, in an attempt to model the activity of the copper containing enzyme tyrosinase. The studies showed that the activities depend on four parameters: the nature of the ligand, the nature of counter anion, the nature of solvent and the concentration of ligand. The Cu(II)-ligands, given here, present the highest catalytic activity (72.920 μmol·L−1·min−1) among the catalysts recently reported in the existing literature.

Biomimetic oxidation of catechol employing complexes formed in situ with heterocyclic ligands and different copper(II) salts

In the present work, catecholase activity is presented. The complexes were prepared by condensation of the organic ligand pyrazolyl L 1 –L 4 and copper(II) ion in situ. The pyrazolyl compounds L 1 –L 4 used in this study are: L 1 is (3,5-dimethyl-pyrazol-1-ylmethyl)-(4-methyl-pyridin-2-yl)-pyrazol-1-ylmethyl-amine; L 2 is 1-{4-[(3,5-dimethyl-pyrazol-1-ylmethyl)-pyrazol-1-ylmethyl-amino]-phenyl}-ethanone; L 3 is 1-{4-[(3,5-dimethyl-pyrazol-1-ylmethyl)-[1,2,4]triazol-1-ylmethyl-amino]-phenyl}-ethanone, and L 4 is 2-[(3,5-dimethyl-pyrazol-1-ylmethyl)-[1,2,4]triazol-1-ylmethyl-amino]-6-methyl-pyrimidin-4-ol, and copper ions salts Cu(II) are (Cu(CH3COO)2, CuCl2, Cu(NO3)2 and CuSO4). In order to determine factors influencing the catecholase activity of these complexes, the effect of ligand nature, ligand concentration, nature of solvent and nature of counter anion has been studied. The best activity of catechol oxidation is given by the combination formed by one equivalent of ligand L 2 and one equivalent of Cu(CH3COO)2 in methanol solvent which is equal to 9.09 µmol L−1 min−1. The Michaelis–Menten model is applied for the best combination, to obtain the kinetic parameters, and we proposed the mechanism for oxidation reaction of catecholase.

Electrostatic balance between global repulsion and local attraction in reentrant polymerization of actin

Actin polymerization depends on the salt concentration, exhibiting a reentrant behavior: the polymerization is promoted by increasing KCl concentration up to 100 mM, and then depressed by further increase above 100 mM. We here investigated the physical mechanism of this reentrant behavior by calculating the polymerization energy, defined by the electrostatic energy change upon binding of an actin subunit to a filament, using an implicit solvent model based on the Poisson-Boltzmann (PB) equation. We found that the polymerization energy as a function of the salt concentration shows a non-monotonic reentrant-like behavior, with the minimum at about 100 mM (1:1 salt). By separately examining the salt concentration effect on the global electrostatic repulsion between the like-charged subunits and that on the local electrostatic attraction between the inter-subunit ionic-bond-forming residues in the filament, we clarified that the reentrant behavior is caused by the change in the balance between the two opposing electrostatic interactions. Our study showed that the non-specific nature of counterions, as described in the mean-field theory, plays an important role in the actin polymerization. We also discussed the endothermic nature of the actin polymerization and mentioned the effect of ATP hydrolysis on the G-F transformation, indicating that the electrostatic interaction is widely and intricately involved in the actin dynamics.

General trends in concentration and temperature behavior of equivalent conductance of N,N-diallylammonium polymers aqueous solutions: Effect of counterion nature and amine structure

The specific and equivalent conductivity of the diluted aqueous solutions of diallyammonium polyelectrolytes, initial monomers (N,N-diallylammonium trifluoroacetate, N,N-diallyl-N-methylammonium trifluoroacetate, N,N-diallyl-N,N-dimethylammonium chloride), and also potassium trifluoroacetate and trifluoroacetic acid solutions are studied. The limiting ionic mobility of diallylammonium cations and trifluoroacetate anion are found. The regularities of concentration changes in the equivalent conductance of polyelectolytes solutions are established. The degree of dissociation of diallyammonium polymers is shown to depend both on the counterion nature and on the amine structure.

Effect of the nature of counterion on the micellar properties of cationic surfactants: a conductometric study

ABSTRACTInteraction of cationic surfactants, tetradecyltrimethylammium bromide (TTAB) and tetradecyltrimethylammonium chloride (TTAC) with anionic dye, tartrazine in aqueous solution has been investigated employing conductometric technique. The free energy of transfer of hydrophobic chain, , surface contribution, and their transfer values, and , free energy, , enthalpy, , and entropy, of micellisation have been calculated. A marked decrease in the critical micelle concentration for TTAB compared to TTAC indicates dramatic role of the smaller counterion Br− over the bigger counterion Cl−. Formation of dye–surfactant ion-pairs which behave as nonionic surfactant has been proposed. Higher negative and positive values for TTAB than TTAC are attributed to difference in the size and nature of the counterions Br− and Cl−. Negative and values clearly suggest that micellisation of TTAB and TTAC is thermodynamically spontaneous and exothermic in nature. As ), it suggests that the process of micellisation is entropy dominated for the two surfactants.

Counter-Ion Effect on the Thermodynamics of Cr(III) Exchange by Macroporous Amberlyst-15

Abstract In the present study, we have investigated the counter-ion effect on the thermodynamics of Cr(III) sorption by macroporous resin Amberlyst-15. The exchange reaction was studied as a function of concentration of Cr(III) and nature of counter-ions at different temperatures. It was observed that nature of counter-ions have a profound effect on the exchange of Cr(III) ions. The selectivity of Amberlyst-15 towards metal ion sorption follows the order univalent>divalent> trivalent forms. This trend can be associated to the electrostatic interaction of ions with the functional sites of the resin. The equilibrium pH values (pHeq) were observed to decrease with Cr3+/H+ exchange whereas an increase in pHeq was detected during the exchange of Cr3+/Li+, Cr3+/Na+, Cr3+/Ca2+ and Cr3+/Al3+. Different adsorption models such as Dubinin–Radushkevich (D–R) and Langmuir were employed to analyze the sorption data. The maximum exchange capacities (X m ) and binding energy constants (K b ) values were determined by using the Langmuir model. The values of both ΔHo and ΔSo were found positive inferring that the exchange process is endothermic accompanied by the dehydration of Cr(III) ions. The thermodynamic parameters revealed that the mechanism of Cr(III) sorption for all the counter ions is entropy driven ion exchange.

Self-Assembly of Hyperbranched Protic Poly(ionic liquid)s with Variable Peripheral Amphiphilicity

Abstract We demonstrated that the aggregation behavior of hyperbranched amphiphilic protic poly(ionic liquid)s (HBP-ILs) can be controlled by varying not only the number of peripheral hydrophobic arms and nature of counterions. Additionally, increasing the hydrophobicity of the HBP-ILs led to a condensed monolayer phase at the air-water interface. The balance of intermolecular interactions mediated by the presence of the ionic liquid component in the inner shell of micelles determines the final morphology in solution and at interfaces.

Tuning Thermoresponsive Properties of Cationic Elastin-like Polypeptides by Varying Counterions and Side-Chains.

We report the synthesis of methionine-containing recombinant elastin-like polypeptides (ELPs) of different lengths that contain periodically spaced methionine residues. These ELPs were chemoselectively alkylated at all methionine residues to give polycationic derivatives. Some of these samples were found to possess solubility transitions in water, where the temperature of these transitions varied with ELP concentration, nature of the methionine alkylating group, and nature of the sulfonium counterions. These studies show that introduction and controlled spacing of methionine sulfonium residues into ELPs can be used as a means both to tune their solubility transition temperatures in water using a variety of different parameters and to introduce new side-chain functionality.

Palladium(II) pyrazolyl–pyridyl complexes containing a sterically hindered N-heterocyclic carbene moiety for the Suzuki-Miyaura cross-coupling reaction

Cationic palladium complexes stabilized by a tridentate neutral {N,N,C} ligand containing a sterically hindered N-heterocyclic carbene (NHC) moiety have been prepared and characterized. The nature of the anionic counterion in the palladium complex has been varied to get crystals suitable for X-ray diffraction. The square planar structure of one of these complexes along with the axial contribution of the sterically hindered NHC fragment has been confirmed by X-ray analysis. In addition, all the isolated [{κ3-N,N,C}PdIICl]+X− [X−=Cl, PF6, BF4, B(C6H3Cl2)4] ion pairs have been scrutinized as catalysts in the cross-coupling Suzuki-Miyaura reaction between phenylboronic acid and variably substituted halo-aryl acceptors. Selected issues from this series have shown improved catalyst turn-over frequencies (TOFs) with respect to structurally related catalytic systems of the state-of-the-art.

Preliminary investigations on a simple polyelectrolyte derived from (CH2CH2C(COOH)2)n: Unexpected solubility-insolubility pattern controlled selectively by the nature of the alkali counterion

Monodisperse samples of alkali poly(trimethylene-1,1-dicarboxylate) polyelectrolytes of (CH2CH2C(COO−)2)n structure and of low to moderate molecular weights have been synthesized and characterized. These polymers are densely and evenly decorated by carboxylate groups, with the anionic moieties extending symmetrically in transverse directions on every third carbon alongside the backbone. In sharp contrast to other polyelectrolytes, they easily precipitate with sodium and potassium ions in water. The precipitation is selective, the solubility varying with the nature of the alkali cation in the order: Li+ > K+ > Na+. Precipitation is fast and reversible, the solubility-insolubility transition being rapidly crossed in both directions when the proper alkali ion is added in excess to the solution/suspension. Experimental investigations (WAXS, FTIR) on the precipitated polymer and DFT theoretical calculations on model 1:1 complexes of malonate subunits with alkali cations have been carried out in order to cast some light on the above phenomena. In addition, a model molecule (CH3C(COOH)2CH2CH2C(COOH)2CH3) has been prepared, supporting the structure of the obtained polyelectrolyte as well as the formation of specific structures at half-deprotonation of the poly(carboxylic acid).

Dependence of solar cell performance on the nature of alkaline counterion in gel polymer electrolytes containing binary iodides

Performance of dye-sensitized nano-crystalline TiO2 thin film-based photo-electrochemical solar cells (PECSCs) containing gel polymer electrolytes is largely governed by the nature of the cation in the electrolyte. Dependence of the photovoltaic performance in these quasi-solid state PECSCs on the alkaline cation size has already been investigated for single cation iodide salt-based electrolytes. The present study reports the ionic conductivity dependence on the nature of alkaline cations (counterion) in a gel polymer electrolyte based on binary iodides. Polyacrylonitrile-based gel polymer electrolyte series containing binary iodide salts is prepared using one of the alkaline iodides (LiI, NaI, KI, RbI, and CsI) and tetrapropylammonium iodide (Pr4NI). All the electrolytes based on binary salts have shown conductivity enhancement compared to their single cation counterparts. When combined with Pr4NI, each of the Li+, Na+, K+, Rb+, and Cs+ cation containing iodide salts incorporated in the gel electrolytes has shown a room temperature conductivity enhancement of 85.59, 12.03, 12.71, 20.77, and 15.36%, respectively. The conductivities of gel electrolytes containing binary iodide systems with Pr4NI and KI/RbI/CsI are higher and have shown values of 3.28, 3.43, and 3.23 mS cm−1, respectively at room temperature. The influence of the nature of counterions on the performance of quasi-solid state dye-sensitized solar cells is investigated by assembling two series of cells. All the binary cationic solar cells have shown more or less enhancements of open circuit voltage, short circuit current density, fill factor, and efficiency compared to their single cation counterparts. This work highlights the importance of employing binary cations (a large and a small) in electrolytes intended for quasi-solid state solar cells. The percentage of energy conversion efficiency enhancement shown for the PECSCs made with electrolytes containing Pr4NI along with Li+, Na+, K+, Rb+, and Cs+ iodides is 260.27, 133.65, 65.27, 25.32, and 8.36%, respectively. The highest efficiency of 4.93% is shown by the solar cell containing KI and Pr4NI. However, the highest enhancements of ionic conductivity as well as the energy conversion efficiency were exhibited by the PECSC made with Li+-containing binary cationic electrolyte.

Hierarchical honeycomb-structured films by directed self-assembly in "breath figure" templating of ionizable "clicked" PH3T-b-PMMA diblock copolymers: an ionic group/counter-ion effect on porous polymer film morphology.

The self-assembly of 1,2,3-triazole and ionic 1,2,3-triazolium "clicked" poly(3-hexylthiophene)-b-poly(methylmethacrylate) (P3HT-b-PMMA) rod-coil diblock copolymers was used to fabricate honeycomb-patterned porous films via "breath figure" templating. The surface and inner morphologies of the honeycomb films can be both controlled by either ionizing the 1,2,3-triazole linker or changing the counter-ion nature.

The effect of counterion in polymer sulfonates on the synthesis and properties of poly-3,4-ethylenedioxythiophene

The electrochemical polymerization of 3,4-ethylenedioxythiophene (EDOT) in the presence of the salt and acid forms of polymer sulfonates with different polymer-chain flexibility is studied. The dependence of the rate of synthesis of poly(3,4-ethylenedioxythiophene) (PEDOT) on the nature of polysulfonate counterion that determines the type and distribution density of the charge in the polyelectrolyte chain is demonstrated. For the Н+ form of a rigid-chain polysulfonate, it is found that the specific interactions between parts of its macromolecules lead to destabilization of EDOT•+ radical cations, hinder the growth of PEDOT chains, and favor the formation of structures with the high degree of charge localization.