Effect of the pH, the concentration and the nature of the buffer on the adsorption mechanism of an ionic compound in reversed-phase liquid chromatography. II. Analytical and overloaded band profiles on Symmetry-C18 and Xterra-C18

In a previous report, the influence of the pH, the concentration, and the nature of the buffer on the retention and overloading behavior of propranolol (pKa = 9.45) was studied on Kromasil-C18 at 2.75 < pH < 6.75, using four buffers (phosphate, acetate, phthalate, and succinate), at three concentrations, 6, 20, and 60 mM. The results showed that the propranolol cation was eluted as an ion-pair with the buffer counter-anion. A similar study was carried out with Symmetry-C18 and Xterra-C18. Two additional buffers, formate and citrate, were also used. Propranolol elution band profiles were recorded for a small (less than 1 microg) and a large (375 microg) sample size. The results are similar to those obtained with Kromasil and confirm earlier conclusions. The buffer concentration, not its pH, controls the retention time of propranolol, in agreement with the chaotropic model. The retention factor depends also on the nature of the buffer, particularly on its valence, and on the hydrophobicity of the basic anion. With the monovalent anions HCOO- (pH 3.75), H2PO4- (pH 2.75), HOOC-Ph-COO- (pH 2.75), HOOC-CH2-CH2-COO- (pH 4.16), CH3COO- (pH 4.75) and HOOC-CHCOOH-COO- (pH 3.14), at moderate loadings, and for the two larger buffer concentrations, the band profiles are well accounted for by a simple bi-Langmuir isotherm model (no adsorbate-adsorbate interactions). By contrast, these profiles are accounted for by a bi-Moreau isotherm model (i.e., with significant adsorbate-adsorbate interactions) with the bivalent anions -OOC-Ph-COO- (pH 4.75), -OOC-CH2-CH2-COO- (pH 5.61), HPO4(2-) (pH 6.75), and HOOC-CHCOO(-)-COO- (pH 4.77) and with the trivalent anion -OOC-CHCOO(-)-COO- (pH 6.39). The best values of the isotherm parameters were determined using the inverse method. The saturation capacity and the equilibrium constant on the low-energy sites increase with increasing buffer concentration, a result consistent with the formation in the mobile phase of a hydrophobic complex between the propranolol cation and the buffer anion. With bivalent and trivalent anions, adsorbate-adsorbate interactions are strong on the low-energy sites but they remain negligible on the high-energy sites. The density of the high energy sites is lower and the equilibrium constant on the low-energy sites are both higher with the bivalent and the trivalent buffer anions than with the univalent buffer anions. These results are consistent with the formation of a 2:1 and a 3:1 propranolol-buffer complex with the bivalent and the trivalent anions, respectively.     

Determination of the single component and competitive adsorption isotherms of the 1-indanol enantiomers by the inverse method

The inverse method of isotherm determination consists in calculating the numerical values of the coefficients of an isotherm model that give a set of chromatographic profiles in best possible agreement with the set of experimental profiles available. This method was applied to determine the adsorption isotherms of the 1-indanol enantiomers on a cellulose tribenzoate chiral stationary phase. Both single-component and competitive isotherms were determined by using no more than one or two overloaded band profiles. The isotherms determined from the overloaded band profiles agreed extremely well with the isotherms determined by frontal analysis. Several isotherm models were used and tested. The best-fit isotherm was selected by means of statistical evaluation of the results. The results show that the adsorption is best characterized with a model describing heterogeneous adsorption with bimodal adsorption energy distribution.     

Organic Syntheses Without Solvent: Preparation of Alkoxyphthalimides and of Alkoxylamines

Alkoxyphthalimides are prepared by alkylation of N-hydroxyphthalimide under solid-liquid phase transfer catalysis without solvent. When conversion of alkoxyphthalimides into alkoxylamines is nearly complete, neat hydrazine hydrate is added at room temperature.     

Synthesis and structure–property relationship of carbazole‐alt‐benzothiadiazole copolymers

A series of four π‐conjugated carbazole‐alt‐benzothiadiazole copolymers (PCBT) were prepared by Suzuki cross‐coupling reaction between synthesized dibromocarbazoles as electron‐rich subunits and 4,7‐bis(4,4,5,5‐tetramethyl‐1,3,2‐dioxaborolan‐2‐yl)?2,1,3‐benzothiadiazole as electron‐deficient subunits. The subunits were directly linked through 2,7‐ or 3,6‐ positions of the carbazole. In addition, the carbazole monomers have been N‐substituted by a branched or a linear side‐chain. The chemical structure of the copolymers and their precursors was confirmed by NMR and IR spectroscopies, and their molar masses were estimated by SEC. Thermal analysis under N₂ atmosphere showed no weight loss below 329°C, and no glass transition was observed in between 0 and 250°C. The band gaps of all PCBTs evaluated by optical spectroscopies and by cyclic voltammetry analysis were consistent with expectations and ranged between 2.2 and 2.3 eV. Finally, 2,7 and 3,6 linkages were shown to influence optical properties of PCBTs. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2059–2068     

Existence and uniqueness of optimal dynamic pricing and advertising controls without concavity

We consider a pricing and advertising dynamic-optimization problem where the goodwill dynamics evolve à la Nerlove–Arrow. The firm maximizes its profit over a finite-planning horizon corresponding to the product’s lifespan, and it turns out that the Hamiltonian is non-concave. We show the existence and uniqueness of an optimal solution under some mild conditions.     

Intra‐ and inter‐supramolecular complexation of poly(butyl methacrylate)‐co‐2‐(1,2,3‐triazol‐4‐yl)pyridine copolymers induced by CoII,FeII, and EuIII ions monitored by molecular hydrodynamics methods

Poly(butyl methacrylate) copolymers embedding bidentate 2‐(1,2,3‐triazol‐4‐yl)pyridine (trzpy) chelating units as comonomer in the side chains were synthesized by controlled radical addition‐fragmentation transfer (RAFT) polymerization. Intracomplexation and intercomplexation of the macromolecules of the poly(butyl methacrylate) copolymers containing 20 % mol of trzpy units induced by Co^II, Fe^II, and Eu^III ions were studied in the solutions by macromolecular hydrodynamics methods. The sedimentation velocity of extremely diluted copolymer solutions and the dynamic viscosity of moderately diluted solutions were studied in a wide range of the salts concentrations. Differences were observed with respect to the copolymer behavior in the presence of the Co²⁺, Fe²⁺, Eu³⁺ ions. These differences are namely due to the differences in the number of coordination bonds required for complex formation and not explicitly to the nature of the corresponding anions. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2632–2639     

The measurement of the magnetic susceptibility of some elements (Fe,Co, Ni,Ge, Sn,Te) in the liquid state

A magnetic balance was used for measuring the susceptibility of metals and alloys, in an atmosphere of purified argon, up to 1800°c.

Comparison of the susceptibilities of liquid Fe, Co and Ni gives information on the liquid state. The changes in the susceptibilities of Ge, Sn and Te on melting are typical of semi-metallic elements and semiconductors, but their behaviour differs according to the degree of symmetry in the solid state.