Comparison of the relationships between the retention of dansyl derivatives of aliphatic amines and eluent composition for normal-and reversed-phase liquid-solid TLC systems

Summary Dansyl derivatives of four long-chain primary aliphatic amines and five secondary aliphatic amines were chromatographed in two adsorption systems: heptane+diisopropyl ether — silica and water+methanol — octadecyl cilica. In the normal-phase system R_M (log k) values were approximately linearly dependent on the log concentration of diisopropyl ether in the eluent; the separation selectivity of dansyl C₈–C₁₂ primary amines was poor. For the reversed-phase system the derivatives of both primary and secondary amines were well separated, the log k values being linearly dependent on per cent concentration of methanol in the eluent.     

Donor-acceptor complex chromatography preparation of a chemically bonded acceptor-ligand and its chromatographic investigation

Summary The preparation of a TNF-phase for HPLC is described. From chemical and chromatographic evaluation it is concluded that chromatographic separation is the result of donor-acceptor complex formation. These findings are supported by the results of an investigation of solvent and temperature effect on retention. For solvent effects two models are discussed. According to the first model based on Fialkov and Borovikov a linear plot is obtained for log k against 1/ for 1/<0.4. In the second model it is shown that the Mass Law is appropriate to describe the solvent effect of binary mixtures of n-hexane and some polar component. Plots of k against 1/[S]^0.5 yield straight lines in all cases and the stoichiometry of complex formation is discussed. The slopes of the lines could be shown to be a measure of solvent strength and are found to parallel Snyder's parameters. From the temperature dependence of log k using the van't Hoff relationship changes in H for complex formation are obtained.     

Mixing effects on the protonation of some polycarboxylates in NaClaq + KClaq at different ionic strengths

Protonation constants of succinic, 1,2,3-propanetricarboxylic and 1,2,3,4-butanetetracarboxylic anions were determined in NaCl_aq + KCl_aq mixtures, at three ionic strengths, I = 1.2, 3 and 4.5 mol L⁻¹. Experimental evidences showed that the function log K^H = f(y) (y = [Na⁺]/([Na⁺] + [K⁺])) is not linear, indicating mixing effects on the protonation constants. The Guggenheim zeroth approximation holds that the above function can be written as:

     

Chromatographic Evaluation of the Lipophilic Properties of Selected Pesticides

Monolinuron, chlortoluron, diuron, isoproturon, linuron, diflubenzuron, dimefuron, teflubenzuron, and lufenuron have been chromatographed on an RP-HPLC column and on RP-HPTLC plates with methanol–water in different volume proportions as mobile phases. The retention values log k, and R_M were extrapolated to zero methanol content. Chromatographic lipophilicities (log k_w, R_Mw, _o(HPLC), and _{o (TLC)}) were compared with measured (log P_exp) partition coefficients and with values (A log Ps, IA log P, C log P, log P_Kowin, and x log P) calculated by use of five different software products. The most significant correlations were found between the chromatographic lipophilicities and C log P values. Satisfactory linear correlation was also obtained between lipophilicity (log k_w, R_Mw) and the valence Gutman index (M).     

Effect of the eluent composition in HPLC on the retention of bi- and trifunctional aromatic solutes

Summary Adsorption equilibria of aromatic compounds containing two or three polar groups (NH₂, OH, NO₂, CN, aromatic nitrogen) are investigated by high-performance liquid chromatography in chromatographic systems consisting of silica and a binary mobile phase consisting of heptane and a polar modifier (isopropanol or 1,4-dioxane). The relationships between the log k values and the concentration of the modifier (expressed as the logarithm of its mole fraction) are interpreted from the basis of the assumed molecular mechanism of adsorption, including solvation effects, i.e., solute-modifier interactions. Correlation of the log k values obtained for the two modifiers indicates that proton donor solutes can be retained by the adsorbed monolayer of dioxane molecules due to an interaction with the exposed ether oxygen atoms.     

Formation constants in the ternary systems: CuII-dipeptideamino acids

Summary A potentiometric titration technique has been used to determine formation constants for the various complexes of Cu^II with amino acids (L) and dipeptides (B) at 298 K and I-0.1 M (NaClO₄). The structure and mode of bonding in binary and ternary complexes are discussed. Values of log are evaluated. The plots of pK of amino acidsversus log K for the present and the earlier known systems gave an empirical relation: pK=–5.3 log K+10.5.     

A study on the fluoride complexes of plutonium(III), samarium(III) and bismuth(III) using fluoride ion-selective potentiometry

Stability constants of the fluoride complexes of Pu(III), Sm(III) and Bi(III) in 1.0M NaClO₄/HClO₄ medium at 23±1°C have been determined by potentiometry using a fluoride ion-selective electrode. Plutonium was reduced to the trivalent state using quinhydrone with an excess to serve as holding reductant. The log values of concentration stability constants log ₁, log ₂, and log ₃ are 3.58, 6.40 and 12.61 for Pu(III), 3.23, 5.81 and 10.54 for Sm(III) and 3.69, 6.13 and 11.04 for Bi(III), respectively. The log ₂ values in all these cases have very large deviation and may be taken only as rough estimates.     

The effect of substitution on the properties of a chemical group

The effect of the substituent R(R = F, OH, NH₂, CH₃) on the electron distribution of the C=C group of ethylene and acrylonitrile may be fairly well represented in terms of classical interactions between the and components of this group and the molecular remainder. A distinction between direct and indirect effects is made, and an estimate of the relative importance of conjugative versus inductive effects is done.This analysis has been performed on a set of 22 SCF wavefunctions calculated with the 4-31G basis set.     

Thermodynamic quantities for the interaction of H+ and Na+ with C2H3O 2 − and Cl− in aqueous solution from 275 to 320°C

The aqueous reactions, {ie865-1}were studied as a function of ionic strength at 275, 300, and 320°C using a flow calorimetric technique. Log K, H and S values were determined from the fits of the calculated and experimental heats while Cp values were calculated from the variation of H values with temperature. The log K and H values for the first two reactions agree well with literature values at these temperatures. No previous results have been reported for the third reaction. The use of equations containing identical numbers of positive and identical numbers of negative charges on both sides of the equal sign (isocoulombic reaction principle) was applied to the log K values determined in this study. The resulting plots of log K for the isocoulombic reactions vs. I/T were approximately linear, which demonstrates that the Cp values for these reactions are approximately zero.Deceased 5 September 1987     

Convergence of retention for small solutes in reversed-phase liquid chromatography

Summary It is shown theoretically that when the concentration of organic solvent in the mobile phase increases, or solute size decreases, log k values of small solutes in reversed-phase liquid chromatography (RPLC) will tend to have a minimum value called the convergence point. A theoretical model for evaluating the convergent coordinates of small solutes is presented by using a stoichiometric displacement model for retention (SMDR). The physical meaning of the coordinates of each kind of convergence are also elucidated. The convergence points have either two-dimensional coordinates with a common ordinate (the logarithm of the phase ratio of the column, log ) or threedimensional corrdinates with two common axes: — log and the logarithm of the molar concentration of the pure displacing agent in mobile phase, log a_D. The other axis relates to the nature of the solutes, such as carbon number of a homolog, van der Waal's surface area, hydrophobic fragment constant etc. for the latter and those and/or concentration axis for the former. The model was tested with published data and found to give a good fit.     

Influence of solvents on the properties of chemical compounds

Based on Sinanolu's solvent theory in connection with a method for the calculation of the molecular volume given by Beveridge a modified continuum model is suggested. The model is tested by the determination of the conformational structure of the title compounds. The predictions obtained by this model are in good agreement with the experimentally determined data.     

Influence of 2,2'-bipyridyl on the stability of Cu2+ -glycine-1:1 complexes

The stability constant of the Cu²⁺-2,2′-bipyridyl-glycine complex (log K = 7,88) was measured and compared with that of the binary Cu²⁺-glycine complex (log K = 8,27). The value Δ log K = ?0,4 (cf. equation (3)) is in the order which should be expected for the coordination of a mixed O? N-ligand to (Cu-Bipy)²⁺ which results in the formation of a ternary complex (cf. [1]).     

Novel enhancement effect of a proton donor on chelate extraction: Extraction of iron(III) with acetylacetone and 3,5-dichlorophenol

Effect of 3,5-dichlorophenol (DCP) on the extraction of Fe(III) with acetylacetone (Hacac) in nonpolar organic solvents has been studied. It is found that a mixture of Hacac and DCP in heptane gives much higher extraction of Fe(III) than Hacac alone. Such novel enhancement effect is ascribable to the association of tris(acetylacetonato)iron(III) [Fe(acac)₃] with DCP in the organic phase by hydrogen bonding. Association of Hacac with DCP has also been investigated and the intrinsic extraction equilibrium of Fe(III) is analyzed by using the equilibrium concentration of free Hacac and DCP. The association complexes are found to be Fe(acac)₃ · n DCP (n=1, 2, 3) in heptane, and the overall association constants (_{ass, n}) are determined to be log _{ass, 1} = 3.41, log _{ass, 2}, = 5.97 and log _{ass, 3}, = 7.50.     

Thermodynamic protonation constants of vardenafil by the nonlinear regression of multiwavelength pH-spectrophotometric titration data

pH-spectrophotometric titration data were used to determine protonation constants of vardenafil at different ionic strengths I and temperatures of 25°C and 37°C. The use of two different multiwavelength and the multivariate treatment of spectral data, SPECFIT32 and SQUAD(84) nonlinear regression analyses and INDICES factor analysis is presented. The reliability of the protonation constants of the drug was proven with goodness-of-fit tests of the pH-spectra. The thermodynamic protonation constants log K _T ⁱ were estimated by a nonlinear regression of (log K, I) data using the Debye-Hückel equation, yielding log K ₄ ^T = 3.59(1) and 3.26(1), log K ₃ ^T = 5.64(1) and 5.81(1), log K ₂ ^T = 9.41(1) and 8.59(2), log K ₁ ^T = 10.92(2) and 10.05(1) at 25°C and 37°C, where the figure in brackets is the standard deviation in last significant digit. Concurrently, the experimental determination of four thermodynamic protonation constants was combined with the computational prediction of the MARVIN program based on knowledge of the chemical structures of the drug and was in good agreement with its experimental value. The factor analysis of spectra in the INDICES program predicts the correct number of light-absorbing components when the instrument error is known and when the signal-to-error ratio SER is higher than 10.      

Amphoteric polystyrene latex colloids: polymerization pathway and the control of particle size and potential

Amphoteric polystyrene latex colloids were prepared by the emulsifier-free emulsion polymerization of styrene. Two co-monomers, methacrylic acid (MA) (anionic) and dimethyl aminoethyl methacrylate (DMAM) (cationic) were used to promote the amphoteric nature of the resultant surfaces. Parameters such as particle size and the isoelectric point (IEP) were measured as a function of polymerization recipe. Particle size decreased with increasing initiator concentration according to the equation: log [d _w]=–0.67 log [I] + 0.316 whered _w is the weight average particle diameter andI is the concentration of initiator (potassium persulphate).The particle size also decreased with increasing temperature, increasing pH and addition of surfactant. Particle size was unaffected by the methacrylic acid content. The isoelectric point pH was decreased on decreasing initiator concentration and on increasing methacrylic acid content.The polymerization pathway was deduced to involve the cationic DMAM during the initiation phase and to involve the anionic MA as well as styrene, during the growth stage. A full polymerization pathway involving the formation of oligomeric DMAM micelles was postulated.     

Predicting 1-octanol-water partition coefficient by high-performance liquid chromatography gradient elution

The method to predict 1-octanol-water partition coefficients (K _ow) from capacity factors (k) obtained by Reversed-Phase High-Performance Liquid Chromatography (RP-HPLC) has been extended to use gradient elution rather than isocratic elution. The mobile phase has been changed either linearly or exponentially with time. The initial composition of the mobile phase and its rate of change affected the log K _ow versus log k relation. This relation was exponential in linear gradient experiments. For non-linear gradient elution in which the water fraction of the mobile phase decreased exponentially from 100% to approach 0% asymptotically, a physically-based equation describing the dependence of log K _ow on log k has been derived. Without any preliminary estimation, RP-HPLC gradient elution allows a precise prediction of log K _ow over a range of nearly six orders of magnitude.     

Voltammetric study of copper(I) thioacetamide complexes

Summary The composition and stability of copper(I) complexes with thioacetamide (TAA) have been evaluated with the help of square-wave voltammetry using the fast pulse technique. Two species, namely Cu(I) (TAA) and Cu(I) (TAA)₂, have been identified having the formation constants log ₁=16.85; log ₂=18.03. The complex is stable in highly acidic medium (pH1). The application for the determination of copper is pointed out.     

A solution study of complex formation between iron(III) and oxalate in dimethylsulphoxide

Summary The complex formation between iron(III) and oxalic acid (ethanedioic acid, H₂ox) has been studied by potentiometry in dimethylsulphoxide (dmso) solution. H₂ox behaves as a weak diprotic acid in such a solvent, with overall association constants: log _j1=8.551(3) and log _j2=14.242(3) at 25°C and 0.1 Mn-Bu₄NClO₄. A reliable set of overall stability constants for the iron(III)-oxalato complexes, log ₁₁=13.16(4), log ₁₂=23.66(4) and log ₁₃=30.75(4), have been obtained for the first time under identical conditions. The electrochemical behaviour of such complexes was studied in dmso at a platinum electrode. The coordination ability of oxalate towards iron(III) in dmso and water media is compared and discussed in the light of thermodynamic and structural parameters.