Enhancement of Demasking of Fluoride Ion From its Aluminum Complexes by Dilution in the Determination With a Fluoride Ion-Selective Electrode

Abstract

In the determination of fluoride ion with an ion-selective electrode the permissible concentration of aluminum increases markedly with decreasing the fluoride concentration in 0.5M citrate buffer solutions at pi I 6. As the accuracy is constant over a concentration range down to 10^?5 M F^? where a Nernstian relation holds fluoride determinations can be accomplished by the successive dilution method. The dilution steps are repeated until the last two results are in agreement, while the concentration of citrate is kept constant. As the ionic strength is kept constant with citrate, the addition of sodium chloride to the buffer is not necessary. Several samples, especially glasses, have been analyzed successfully.     

The hall effect in molten salts

Abstract

The Hall Effect is measured in the molten ionic salts CuCl, AgCl and AgBr. Values of 0.023, 0.031 and 0.027 cm²/volt sec are obtained for the effective mobility. The values obtained are one or two orders of magnitude larger than drift mobilities and so indicate there can be no correspondence between Hall and drift mobilities in molten salts. These measurements appear to be the first of the Hall Effect in molten ionic salts     

Interactions of Nile Blue Sulphate with Nucleic Acids as Studied by Resonance Light-Scattering Measurements and Determination of Nucleic Acids at Nanogram Levels

ABSTRACT

The interactions of nile blue sulphate (NBS) with nucleic acids, including calf thymus DNA, fish sperm DNA and yeast RNA, were characterized with resonance light-scattering (RLS) measurements by using a common spectrofluorometer. Accordingly a method for the determination of nucleic acids at nanogram levels was established. At pH's of 7.20～7.60 and ionic strengths lower than 0.012, the interactions of NBS with nucleic acids result in three characteristic RLS peaks at 293.4 nm, 349.4 nm and 560.4 nm. Mechanism study shows that these peaks are ascribed to the long range assembly of NBS on the molecular surface of nucleic acids, which depends on pH, ionic strength and the stranded structure of nucleic acids. A Scatchard plot was constructed by using the RLS data, yielding the assembly number and assembly constant being 6.4 and 7.13x10⁶ mol^?1 1 for NBS assembly on the molecular surface of calf thymus DNA. The same parameters are 6.6 and 4.58x10⁶ mol^?1 1 for the assembly on that of fish sperm DNA, 3.9 and 1.67x10⁶ mol^?1 1 on that of yeast RNA, respectively. Linear relationships were found between the enhanced RLS intensity at 293.4 nm and nucleic acid concentration. If 1.2x10^?5 mol I^?1 NBS was employed, 0～0.80 μg ml^?1 calf thymus DNA and fish sperm DNA, 0.20～0.60 μg ml^?1 yeast RNA can be determined with the determination limits being 3.2 ng ml^?1 for calf thymus DNA, 11.5 ng ml^?1 for fish sperm DNA and 38.3 ng ml^?1 for yeast RNA, respectively. Four synthetic samples were determined with satisfaction.     

Ion Interaction Chromatographic Separation of Amino Acids Using a Basic-Tetraalkylammonium Salt Mobile Phase

Abstract

A basic mobile phase containing a tetraalkylammonium (R₄N⁺) salt was used to enhance the retention of free amino acids (AA) in their anion form on a polystyrene divinylbenzene copolymeric (Hamilton PRP-1) nonpolar stationary phase adsorbent. Major variables, which can be readily manipulated to alter this retention and resolve complex AA mixtures, are: structure and concentration of R₄N⁺ salt, type and amount of organic modifier in the mobile phase solvent, concentration and selectivity of the counteranion present, and mobile phase pH and ionic strength. Mobile phase gradients based on a pH change, or an ionic strength change and their combination, while all other variables are constant, were evaluated for the separation of complex AA mixtures. Detection was accomplished by absorbance or fluorescence after a post-column ortho-phthalaldehyde reaction.     

Synthesis and evaluation of multitopic bisbenzothiazolyl calix[4]arenes for ionic toxicants

Abstract

Two new benzothiazolyl calix[4]arene-based multitopic molecular receptors L-1 and L-2 have been synthesised and evaluated for recognition of ionic toxicants. The receptors selectively interact with copper, silver and fluoride ion toxicants as assessed through UV-visible, NMR and colorimetric techniques. The stability of L-1:Cu⁺² and L-2:Cu⁺² complexes was found to be higher than that of complexes formed with Ag⁺ and F^– complexes in the presence of trifluoroacetic acid. Superiority of L-1 over L-2 for analysis of identified toxicants has been determined by measurement of binding constants.     

Electrodes Potentiometriques Et Amperometriques a Levures Permeabilisees: Determination Du L-Lactate

Abstract

A biosensor using permeabilized yeasts (Hansenula anomala) is described for the determination of L-lactate. The same electrode can be used either potentiometrically or amperometrically. The linear ranges are respectively of 4.10^?5M to 2.10^?3M for potentiometry and 8.10^?7M to 3.10^?3M for amperometry with a reproducibility and a precision of ± 2 to 3%. The parameters involved in the optimization of electrode response, such as pH, temperature, cofactor concentration and ionic strength of the buffers, are discussed in details for both types of measurements. The amperometric technique is suitable for lactate determinations in biological media. In this case, differential measurements are used in order to eliminate interferences of biological redox reactions.     

Single-Ionic Conductivityin Poly(Sodium 2-Methacryloyl 3-[Ω-Methoxyl Oligo(Oxyethylene)]Propylsulfonate)

Abstract

Sodium 2-methacryloyl 3-[ω-methoxyl oligo(oxyethylene)] propylsulfonate was synthesized, from which homopolymer-based polyelectrolyte was prepared. The polyelectrolytes thus obtained show single Na⁺ionic conductivity at ambient temperature, neither adding plasticizer nor hybridizing small molecular salt. The conductivity depends considerably on the length of oligo(oxyethylene) side-chain. Optimally, the highest conductivity of 6.0 × 10^?6 S/cm at 25°C is obtained when the number of (CH₂CH₂O) repeating units equals 16. Results indicate that the conductivity data follow WLF and VTF equations. The WLF parameters are found to be comparable with “universal” values, and analysis of the configuration entropy model suggests that the conduction of Na⁺ ions is carried out by an association mechanism.     

Precision null-point potentiometry: A simple,rapid and accurate method for low concentration chloride determinations

A new, rapid and accurate potentiometric technique is described for the determination of chloride in the concentration range 10^-6 to 10^-1M. For many samples results can be obtained in less than a minute with 0.1% accuracy. The method consists simply of changing the chloride concentration of an unknown solution, while maintaining the ionic strength constant, until it is of identical concentration to a known reference solution. This can be accomplished experimentally in such a way that temperature control and calculation corrections for chloride from reagents or electrodes are not necessary. The procedure can be set up so that the calculation for the result is merely an addition or subtraction of two numbers. The general principles and simple experimental techniques are described and results for chloride presented.     

Potentiometric and conductometric determination of ammonium by gas-diffusion flow injection analysis

Summary Considerable enhancement of selectivity in the potentiometric and conductometric determination of ammonium is provided by gas-diffusion separation in flow injection analysis. Ammonium and potassium selective liquid membrane electrodes can be used for determinations in the concentration range 10^–7–10^–2 mol/l with high precision and fast sample throughput. No interferences are encountered in the presence of ionic species and molecules that likely adsorb when the sensors are in direct contact with the sample. The selectivity over volatile amines is enhanced due to kinetic discrimination. Conductometric detection is shown to be as sensitive as the potentiometric detection. A major advantage, however, is the linear rather than logarithmic relationship between concentration and conductivity.     

Mean Ionic Activity Coefficients of Alkali Metals Dissolved in High Dielectric Constant Solvents: A Comparison Between Experimental Data and Fuoss Theoretical Data

Abstract

Ionic association of strong univalent symmetrical electrolytes dissolved in Hydrogen Bonded Solvents (HBS) having high dielectric constants, has been studied in terms of mean ionic activity coefficient. This parameter has been analysed with the Fuoss's Paired Ion Model in the concentration range 0.5-500m0lm^-3. The experimental data are consistent with this model. It has been shown that fits to the experimental data could be obtained with fixed values of fraction of contact pain α and Gurney radius corresponding to the Contact Pair (CP). The results of fractions of free ions γ and conducting ions (p) as a function of concentration are also discussed. Conductimetric pairing constants K Lanbad; and Gibbs free energy δG are deduced to explain this ionic association. The iduence of the dielectric constant of the solvent on the ionic association has been also investigated in this work.     

Viscosity Molecular Weight Determination of Polyadenylic Acid

Abstract

In this study viscosity measurements of polyadenylic acid (PolyA) in aqueous solution were carried out under different conditions. In the absence of any additives, the polymer degraded during flow through the capillary of a viscometer or when standing still. Degradation during the former was more severe. The degradation of polyadenylic acid can be prevented by addition of an electrolyte such as KCl to increase the ionic strength. However, in this case the deviation from linearity was still considerable at most ionic strength values. The best fit to the Huggins and Kraemer equations was obtained using a Tris–EDTA buffer solution with a final pH of 7.65. Estimation from intrinsic viscosity and weight-average molecular weight values gave k and α as 2.04 × 10^?5 and 0.89 from the equation η = kM ^α. The difference between Huggins (k ₁) and Kraemer (k ₁′) constants was close to 0.50 for all measurements.     

Supramolecular Ionic‐Liquid Gels with High Ionic Conductivity

Supramolecular ionogels were prepared by the gelation of room‐temperature ionic liquid 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([BMIm][BF₄]) with (S,S)‐bis(leucinol)oxalamide. Remarkably, the ionic conductivity of solutions and ionogels with low gelator concentrations is higher than that of neat [BMIm][BF₄]. On the basis of molecular dynamics simulations and quantum mechanical calculations, the origin of this phenomenon is attributed to the higher affinity of gelator molecules towards [BF₄]^? ions, which reduces the electrostatic attraction between [BMIm]⁺ and [BF₄]^? and thus increases their mobility. With increasing gelator concentration, the ionic conductivity decreases due to the formation of a denser gelator matrix, which hinders the pathways for ionic transport. However, even for very dense ionogels, this decrease is less than one order of magnitude relative to neat [BMIm][BF₄], and thus they can be classified as highly conductive materials with strong potential for application as functional electrolytes.     

Ionic complex of Vanadyl(IV) in the polymerization of 2-hydroxyethyl methacrylate as probed by EPR

The vanadyl ionic complex VO(DMSO)₅(ClO₄)₂ (I) exhibits high catalytic activity in the polymerization of 2-hydroxyethyl methacrylate (HEMA). The changes in the vanadium oxidation state during polymerization under argon and in the presence of oxygen were studied by EPR. Under aerobic conditions, the HEMA chain propagation radical was detected; this indicates the presence of a radical chain polymerization pathway caused by the ability of I to perform one-electron reduction of molecular O₂. The radical generation rate is controlled by the initial concentration of I: its increase results in the formation of inactive species, presumably, μ-peroxo complexes V^v-O-O-V^v. It was shown by kinetic methods that the radical-chain pathway initiated by the reaction of I with O₂ is not crucial in the HEMA polymerization.     

Methods for Reliable pH Measurements of Precipitation Samples

Abstract

Significant errors in precipitation acidity determinations can result from improper use of pH electrodes. Conventional electrodes measure free hydrogen ion activity instead of hydrogen ion concentration or free acidity. Correction from activity to concentration is a function of ionic strength and can be large for the low ionic strengths typical of precipitation samples. Also, differences between sample and standard calibration buffer solution ionic strengths can result in liquid-junction potentials that affect electrode readings. Streaming potentials due to the stirring of precipitation samples can cause the single, largest error in pH. Certain procedures can be employed to reduce individual types of errors. These and methods to assess pH electrode performance are discussed.     

Ionic Association of the Ionic Liquids [C4mim][BF4], [C4mim][PF6], and [Cnmim]Br in Molecular Solvents

Considering the ionic nature of ionic liquids (ILs), ionic association is expected to be essential in solutions of ILs and to have an important influence on their applications. Although numerous studies have been reported for the ionic association behavior of ILs in solution, quantitative results are quite scarce. Herein, the conductivities of the ILs [C_nmim]Br (n=4, 6, 8, 10, 12), [C₄mim][BF₄], and [C₄mim][PF₆] in various molecular solvents (water, methanol, 1‐propanol, 1‐pentanol, acetonitrile, and acetone) are determined at 298.15 K as a function of IL concentration. The conductance data are analyzed by the Lee–Wheaton conductivity equation in terms of the ionic association constant (K_A) and the limiting molar conductance (Λ_m⁰). Combined with the values for the Br^? anion reported in the literature, the limiting molar conductivities and the transference numbers of the cations and [BF₄]^? and [PF₆]^? anions are calculated in the molecular solvents. It is shown that the alkyl chain length of the cations and type of anion affect the ionic association constants and limiting molar conductivities of the ILs. For a given anion (Br^?), the Λ_m⁰ values decrease with increasing alkyl chain length of the cations in all the molecular solvents, whereas the K_A values of the ILs decrease in organic solvents but increase in water as the alkyl chain length of the cations increases. For the [C₄mim]⁺ cation, the limiting molar conductivities of the ILs decrease in the order Br^?>[BF₄]^?>[PF₆]^?, and their ionic association constants follow the order [BF₄]^?>[PF₆]^?>Br^? in water, acetone, and acetonitrile. Furthermore, and similar to the classical electrolytes, a linear relationship is observed between ln K_A of the ILs and the reciprocal of the dielectric constants of the molecular solvents. The ILs are solvated to a different extent by the molecular solvents, and ionic association is affected significantly by ionic solvation. This information is expected to be useful for the modulation of the IL conductance by the alkyl chain length of the cations, type of anion, and physical properties of the molecular solvents.     

Investigation on the extraction of strontium ions from aqueous phase using crown ether-ionic liquid systems

The extraction of strontium ions using DCH18C6 as the extractant and various ionic liquids (ILs) as solvents has been investigated. The distribution ratio of Sr²⁺ can reach as high as 10³ under certain conditions, much larger than that in DCH18C6/n-octanol system. The extraction capacity depends greatly on the structure of ionic liquids. In IIs-based extraction systems, the extraction efficiency of strontium ions is reduced by increasing the concentration of nitric acid and can also be influenced directly by the presence of Na⁺ and K⁺ in the aqueous phase. It is confirmed that the extraction proceeds mainly via a cation-exchange mechanism.     

SURFACE STRUCTURE OF THE MICELLE OK AN AMPHOTERIC AMPHIPHILE DERIVED FROM LYSINE

ABSTRACT

Micelle structure in aqueous colloid of an amphoteric amphiphile N^αN^α-dimethyl-N^? -lauroyl lysine (DMLL), which was derived from lysine, was studied through light scattering, SAXS and a rheological method. The critical micelle concentration of the colloid system is 216 UM and the weight average molecular weight of the micelle is 2.40 × 10⁴, i.e. the aggregation number is 67.4. The diameter of the micelle is about 43.4 Å and the spherical micelle is likely to be retained in a concentration up to about 20 %, The SAXS measurements show that the electron density Fluctuation in the micelle is almost negligible and that the surface area of the micelle is approximately 3.5 times larger than that of a completely smooth sphere.     

The influence of ionic and elastic effects on partial switching in ferroelectric liquid crystal devices

Abstract

The simultaneous influences of elastic stress and ionic fields on switching in ferroelectric liquid crystals are considered. Experiments are performed which show that the combined influences can be quite complex. When a reset pulse is applied, it can enhance or decrease the previous ionic field, as well as change the elastic state of the pixel so that when the reset and switching pulses are close together, the combination of these effects influences the result significantly. In some situations, the outcome from simple partial switching schemes cannot be explained from ionic and elastic effects; we suggest a surface switching effect in this case.     

Macroinitiators of controlled free-radical polymerization of methyl methacrylate that are based on the tributyl boron-naphthoquinone system

Methods of preparing prepolymers with M = (2–5) × 10⁴ via the free-radical polymerization of methyl methacrylate in the presence of tri-n-butyl boron and 1,4-naphthoquinone at 30–45°C are developed. ¹H NMR spectroscopy measurements show that, in the prepolymer, the ratio between the enchained aromatic structures and the monomer units is 3: 1000. The activation energy for the postpolymerization of MMA initiated by the prepolymer is found to be 39.3 kJ/mol, and the molecular mass of the prepolymer is (0.8–1.2) × 10⁶. The effect of small amounts of acrylates and phosphonium salts on the polymerization of methyl methacrylate and the molecular mass of the polymers is investigated. It is demonstrated that, when polymerization is conducted in the presence of ionic liquids at concentrations commensurable with the concentration of aromatic fragments enchained into the prepolymer, the rate of the process decreases.     

Matrix isolation study of the products of the interaction between metastable Ar and Kr atoms and chloroform. Photodecomposition of HCCl+2 and HCCl−2

The emission spectrum of a microwave discharge through argon and the infrared and ultraviolet spectra of the products of the interaction of HCCl₃ with the periphery of such a discharge, observed after radpid quenching in an argon matrix at 14 K, indicate that metastable argon atoms play an important role in matrix isolation experiments using such a discharge configuration to produce free radicals and molecular ions. Exceptionally high yields of HCCL⁺₂ and HCCl^?₂ and a significant concentration of CCl⁺₃ were stabilized in these experiments. The observations support the assignment of the 1037 cm^?1 peak to “isolated” CCl⁺₃. Upon exposure of the sample to 370-280 nm radiation, a prominent, slightly perturbed absorption of ClHCl^? appeared at 705 cm^?1. This absorption was destroyed by 280-260 nm radiation. The relative stability of both HCCl⁺₂ and CCl⁺₃ upon exposure of the sample to radiation of wavelength longer than 280 nm is attributed to electron scavenging by the HCCl₃ in the matrix; this species is present in considerably greater concentration than are the ion products. Evidence is presented for the photodecomposition of HCCl⁺₂ at wavelengths shorter than about 280 nm. A marked increase in the concentration of HAr⁺_n when HCCl⁺₂ was photolyzed by radiation of wavelength shorter than 260 nm is consistent with the calculated threshold energy for proton transfer from HCCl⁺₂ to Ar. The results of krypton matrix experiments are also consistent with this mechanism. Unstructured absorption bands near 285 and 250 nm are tentatively attributed to ClHCl^? and HCCl⁺₂, respectively. An increase in the concentration of “nonrotating” H₂O, compared to H₂O molecules free to undergo rotational transitions, when ions are present in the matrix can be attributed to the electric field producted by ionic interactions.