A temperature study on critical micellization concentration (CMC), solubility, and degree of counterion binding of α-sulfonatomyristic acid methyl ester in water by electroconductivity measurements

 For a sodium salt of α-sulfonatomyristic acid methyl ester (14SFNa), one of the α-SFMe series surfactants, critical micellization concentration (CMC), solubility and degree of counterion binding (β) were determined by means of electrocon-ductivity measurements at different temperatures (at every 5 °C) ranging from 15 to 50 °C. The phase diagram of 14SFNa in pure water was constructed from the CMC- and solubility-temperature data, in which the Krafft temperature (critical solution temperature) was found around 0 °C. The changes in the Gibbs energy, ΔG ⁰ _m, enthalpy, ΔH ⁰ _m, and entropy, ΔS ⁰ _m, upon micelle formation as a function of temperature were evaluated taking βvalues into calculation. Received: 28 August 1996 Accepted: 5 November 1996     

Effect of Variant Counterions on Stability and Particle Size of Silica Sol

The effects of variant counterions with ionic strength of 0.05, 0.10, 0.20 and 0.25 mol·kg^-1 on the stability and particle size of silica sols have been studied using the traditional methods of Ubbelohde viscosity measurement, TEM and titration respectively, finding that the stability and particle size of the silica sols are all concerned with the acidic, positively electric properties and the sizes of the counterions, as well as the attraction between the counterions and surface silicon hydroxyl groups of the silica sols. The small positively charged counterions lead to the decrease in particle sizes, making the silica sol the most stable. But the larger weakly acidic counterions can restrict the particle sizes of the silica sols and easily make the sols coagulate. It was also found that there existed a linear relationship between log r and log η, which has not ever been reported. The effect of temperature on the stability and particle sizes was also discussed.     

Ionic aggregation in random copolymers containing phosphonium ionic liquid monomers

Copolymers of n‐butyl acrylate and phosphonium ionic liquid monomers possessing various alkyl substituents and counterions were synthesized through a combination of conventional free radical copolymerization and anion exchange. Differential scanning calorimetry and dynamic mechanical analysis provided the thermal and mechanical properties of these phosphonium cation‐containing random copolymers. Factors including alkyl chain length of phosphonium substituents, counterion type, as well as ionic concentration significantly influenced the association of phosphonium cations. Phosphonium ionomers with trialkyl substituents on phosphonium cations did not display the characteristic small‐angle X‐ray scattering peak, suggesting the absence of ionic clusters. However, low q peaks in wide‐angle X‐ray diffraction was indicative of significant concentration fluctuations wherein the ionic monomeric units associated. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Conductometry and Thermodynamics Study of Metal Dodecyl Sulfates in Aqueous Solution

The aggregation behavior of metal dodecyl sulfates (MDS), [Na¹⁺, Mg²⁺, Mn²⁺, Co²⁺, and Ni²⁺] in water has been studied by electrical conductivity (at 293.15–333.15 K) and surface tension methods (at 303.15 K). Critical micelle concentrations (CMCs), degree of counterion dissociation (β) evaluated from conductivity data. Using law of mass action model, the thermodynamic parameters viz. Gibbs energy (ΔG_m ⁰), enthalpy (ΔH_m ⁰), and entropy (ΔS_m ⁰) were evaluated. The enthalpy of micellization decreases strongly with increasing temperature. ΔG is always negative (thermodynamically favored process) and slightly temperature and counterion dependent. Gibbs energy and entropy exploit micellization as thermodynamic favorable process. The electrostatic repulsions between ionic head groups, which prevent the aggregation, are progressively screened as the ionic character decreases with the size of the counterion. The plots of differential conductivity, (dk/dc) _T,P , versus the total surfactant concentration enables us to determine the CMC values more precisely than the conventional method. Surfactants with strong condense counterion are adapted to rodlike micelle better than to a spherical micelle. The data are explained in terms of molecular characteristics of surfactants viz. degree of dissociation, polar head group size and counterion.     

Co‐ and Counterion Effect on the Micellization Characteristics of Dodecylpyridinium Chloride

Micellization parameters, critical micelle concentration (cmc), degree of counterion dissociation (α), aggregation number (n), critical packing parameter, and hydrophobic core volume of Dodecylpyridinium chloride (DPC) micelles were determined in presence of varying concentrations of sodium chloride (NaCl), sodium acetate (SAc), sodium propionate (SPr), ethylammonium chloride (EACl), diethylammonium chloride (DEACl), tetraethylammonium chloride (TEACl), and propylammonium chloride (PACl) through conductometric investigations at 298.15 K. The resulting data suggests that both counter and coions affect the cmc values‐cmc depressing tendency of the salts varies in order PACl≈NaCl>EACl>DEACl>TEACl>SPr>SAc, while the degree of counterion dissociation is dependent on the nature and concentration range of the added salt. Increasing salt concentration increases the relative hydrophobic volume of the micelles and coion has not much effect on aggregation number.     

An Approximate Expression for the Degree of Counterion Binding of Dressed Micelles

A simple formula for calculating the degree of counterion binding of dressed micelles is presented. This approximate expression for the spherical micelle is derived from the extending Langmuir's method in the case of high surface potentials. It works quite well for the estimation of the degree of counterion binding of micelles. The simple form is very convenient for practical use.     

Self-Assembly of DNA and RNA Building Blocks Explored by Nitrogen-14 NMR Crystallography: Structure and Dynamics

The isotopic enrichment of nucleic acids with nitrogen-15 is often carried out by solid-phase synthesis of oligonucleotides using phosphoramidite precursors that are synthetically demanding and expensive. These synthetic challenges, combined with the overlap of chemical shifts, explain the lag of nitrogen-15 NMR studies of nucleic acids behind those of proteins. For the structural characterization of DNA and RNA-related systems, new NMR methods that exploit the naturally occurring 99.9 % abundant nitrogen-14 isotope are therefore highly desirable. In this study, we have investigated nitrogen-14 spectra of self-assembled quartets based on the nucleobase guanine in the solid state by means of magic-angle spinning NMR spectroscopy. The network of dipolar proton–nitrogen couplings between neighboring stacked purine units is probed by 2D spectra based on ¹H→¹⁴N→¹H double cross-polarization. Interplane dipolar contacts are identified between the stacked G quartets. The assignment is supported by density functional theory (DFT) calculations of the anisotropic chemical shifts and quadrupolar parameters. The experimental spectra are fully consistent with internuclear distances obtained in silico. Averaging of chemical shifts due to internal motions can be interpreted by semiempirical calculations. This method can easily be extended to synthetic G quartets based on nucleobase or nucleoside analogs and potentially to oligonucleotides.     

Lipophilic counterion effect on aggregation and adsorption behavior of quaternary ammonium surfactants

The obvious different aggregation and adsorption behavior of six newly quaternary ammonium surfactants with different lipophilic counterions has been discoverd by measurements of equilibrium and dynamic surface tension, fluorescence and conductivity. Interestingly, the critical micelle concentration (CMC) and its surface tension γ_CMC decrease with the increasing counterion chain length. However, three methods have confirmed that an exception of CMC increases slightly from C₁₆NC₁ to C₁₆NC₂. According to experimental results, a balanced mechanism between hydrophobicity and electrostatic of counterion is proposed. Besides, the dynamic surface tension results show the diffusion coefficient increases with the increasing counterion length both at a short time (D_t?→?0) and long time (D_t?→?∞), which indicates a faster adsorption process. Unlike the inorganic counterion, the diffusion coefficient decreases with the increase of hydrophobic chain length. This is attributed to the strong electrostatic interactions between counterions and cationic headgroups.     

pePC-SAFT: Modeling of polyelectrolyte systems: 1. Vapor–liquid equilibria

A molecular thermodynamic model for polyelectrolyte systems—called pePC-SAFT—is proposed. The effect of charged monomers within the polyelectrolyte chain is explicitly taken into account in the reference term by replacing the hard-chain contribution of the PC-SAFT model by a charged-hard-chain contribution. Moreover, counterion condensation is accounted for to determine the effective number of charges along the polyion as well as of free counterions. The electrostatic contribution of the free counterions is described by a Debye–Hückel term.     

Synthesis and cross-coupling reactions of tetraalkylammonium organotrifluoroborate salts

Treatment of organoboronic acids with hydrofluoric acid generates an in situ tetracoordinate hydronium organotrifluoroborate species which undergoes counterion exchange with tetra-n-butylammonium hydroxide. The resultant tetraalkylammonium salts are as air and moisture stable as their potassium organotrifluoroborate counterparts with the added advantage of being readily soluble in organic media. They were found to undergo Pd-catalyzed Suzuki–Miyaura cross-couplings with a variety of aryl- and alkenylhalides under mild conditions. Their Pd-catalyzed cross-coupling with acid halides is also possible for the generation of ketones.