Examination of the Origin, Variation, and Proper Use of Expressions for the Estimation of Association Constants by Capillary Electrophoresis

Over the last several decades a variety of techniques have been developed to determine apparent equilibrium constants for molecular association in solution (e.g., to micelles, proteins, cyclodextrins, antibiotics, etc.). The relationships describing binding isotherms appear in several forms and have been given several different names. It is well known that most of these expressions are closely related and that some may be more advantageous than others for experimental or statistical reasons. In the case of electrophoresis, association constants are calculated from the relationship between ligand concentration and the measured electrophoretic mobility of the solute. This relationship has appeared in many forms that have been used numerous times at least since 1951. Recently they have reappeared in identical or slightly rearranged versions in several capillary electrophoresis (CE) studies. Some of these methods require the measurement of the electrophoretic mobility of the solute-ligand complex, a value that often cannot be accurately measured. Some systems require correction or normalization procedures in order to negate any changes in solute mobility that are not due to binding. The relationship between the various expressions that can be used to calculate binding constants with CE is shown. The advantages, limitations and proper use of the various approaches are discussed. Examples are given for both achiral and chiral analytes

Effect of Micelles and Mixed Micelles on Efficiency and Selectivity of Antibiotic-Based Capillary Electrophoretic Enantioseparations

Vancomycin (an oligophenolic, glycopeptide, macrocyclic antibiotic) has been shown to be a superb chiral selector for anionic and neutral compounds. It was found that adding sodium dodecyl sulfate to the run buffer increased efficiency by over 1 order of magnitude, decreased analysis times, and reversed the elution order of the enantiomers. This allows for control of the retention order as well as the resolution of enantiomers in complex mixtures in a single run. A mechanism is proposed which explains all of the observed effects and is verified experimentally. Since vancomycin is present in both the micelle and in free solution, previously proposed micelle-selector models are, at best, limiting cases. A general equation is derived which can be used to describe all possible interactions, including those with the capillary wall, if needed. Also, it is shown that electrophoretic mobilities and not migration times must be used to calculate binding constants of a solute to the micelle, the chiral selector, or both. Furthermore, it is shown that a neutral marker molecule cannot be used to accurately correct mobilities that have been altered due to changes in solution viscosity. While this work utilizes the practical vancomycin-micelle system, the general conclusions and theory apply to most other analogous CE systems as well. © 1995, American Chemical Society. All rights reserved

Mechanism of Signal Suppression by Anionic Surfactants in Capillary Electrophoresis-Electrospray Ionization Mass Spectrometry

Micellar-mediated capillary electrophoresis (CE) is used for a wide variety of applications, including the separation of pharmaceuticals, environmental contaminants, illicit drugs, DNA fragments, and many other biological samples. The electrospray ionization interface is one of the most common CE-MS interfaces. Coupling micellar-mediated CE separations with MS detection combines two very powerful, widely applicable analytical techniques. Some types of surfactants strongly interfere with electrospray ionization mass spectrometric (ESI-MS) detection of analytes, and in many cases the ESI-MS analyte signals are completely quenched. Only a few reports have appeared that describe the ESI-MS detection of analytes in the presence of surfactants; however, the exact mechanism of ionization suppression has not yet been addressed. In this work, a modified aerosol ionic redistribution (AIR) model is presented that qualitatively explains the results of previous studies, including those using polymeric surfactants . Analyte ionization suppression by surfactants appears to be caused by Coulombic interaction between oppositely charged solute and surfactant ions in the ESI-produced offspring droplets. It appears that the ability of surfactants to quench electrospray ionization is directly related to the surface activity and the charge of the surfactant Also, highly surface active components tend to be enriched in ESI-produced offspring droplets. Analyte ion signals can be detected under conditions that lower the surface concentration of oppositely charged surfactant ions in aerosol droplets. The mechanistic information outlined here may be used to design micellar-mediated CE separations that allow detection of anaryte ions by ESI-MS

Highly Enantioselective Capillary Electrophoretic Separations with Dilute Solutions of the Macrocyclic Antibiotic Ristocetin A

Ristocetin A is one of a series of structurally related amphoteric, glycopeptide, macrocyclic antibiotics. These compounds have several features that make them attractive as chiral selectors. These include spatially oriented functional groups that are known to provide the types of interactions that are conducive to enantio-recognition, a somewhat rigid pocket that can provide a site for hydrophobic interactions and polar, flexible arms (i.e., pendent sugar moieties) that can rotate to hydrogen bond and otherwise interact with a variety of chiral analytes. In addition, these compounds are sufficiently soluble in water, aqueous buffers and aqueous-organic solvents that are commonly used in capillary electrophoresis (CE). The use and optimization of ristocetin A as a chiral selector in CE is discussed. Over 120 racemates are resolved including a variety of N-blocked amino acids, non-steroidal anti-inflammatory compounds and a large number of biologically important compounds containing carboxylic acid groups (e.g., mandelic acid derivatives, lactic acid derivatives, folinic acid, tropic acid). © 1995

Capillary Electrophoretic Enantiomeric Separations using the Glycopeptide Antibiotic, Teicoplanin

Teicoplanin is the third in a series of macrocyclic glycopeptide antibiotics that has been evaluated as a chiral selector in capillary electrophoresis (CE). It was used to resolve over 100 anionic racemates at low selector concentrations. Like the other related glycopeptide antibiotics, its enantioselectivity tends to be opposite to that of the ansa-type antibiotics which prefers cationic compounds-particularly amines. Factors that affect teicoplanin-based enantioseparations include the selector concentration, pH, and the concentration of the organic modifier. The temperature and the nature and strength of the buffer are also known to affect the stability of the chiral selector as well as the enantioseparation. Teicoplanin exhibited some features that were not noted with the other glycopeptide antibiotics. For example, it aggregates (forms micelles) in aqueous solutions and this influences its enantioselectivity. Unlike the other studied glycopeptides, teicoplanin precipitates in alcohol-water mixtures. It also binds less to the capillary wall than vancomycin as evidenced by the faster electroosmotic flow velocity. The micellization of teicoplanin is pH dependent so that the effect of pH on enantiorecognition is more complex for teicoplanin than for other chiral selectors. Also it is shown that the simple model proposed to explain the role of organic modifiers in cyclodextrin-based CE enantioseparations may not apply to these and other systems

Activated Carbon Produced from Agricultural Residues

A process for producing activated carbon from agricultural residues by heating the residues to a temperature in the range of about 250° C. to about 550° C. to volatilize organic compounds in the residues and to carbonize the residues and further heating to activate the carbonized residues. Activated carbon produced from agricultural residues

A Magnetic Transition Probed by the Ce Ion in Square-Lattice Antiferromagnet CeMnAsO

We examined the magnetic properties of the square-lattice antiferromagnets CeMnAsO and LaMnAsO and their solid solutions La1-xCexMnAsO by resistivity, magnetic susceptibility, and heat capacity measurements below room temperature. A first-order phase transition is observed at 34.1 K, below which the ground-state doublet of the Ce ion splits by 3.53 meV. It is likely that Mn moments already ordered above room temperature are reoriented at the transition, as reported for related compounds, such as NdMnAsO and PrMnSbO. This transition generates a large internal magnetic field at the Ce site in spite of the fact that simple Heisenberg interactions should be cancelled out at the Ce site owing to geometrical frustration. The transition takes place at nearly the same temperature with the substitution of La for Ce up to 90%. The Ce moment does not undergo long-range order by itself, but is parasitically induced at the transition, serving as a good probe for detecting the magnetism of Mn spins in a square lattice.Comment: 11 pages, 5 figures, to be published in J. Phys. Soc. Jp

Lattice collapse and quenching of magnetism in CaFe2As2 under pressure: A single crystal neutron and x-ray diffraction investigation

Single crystal neutron and high-energy x-ray diffraction have identified the phase lines corresponding to transitions between the ambient-pressure tetragonal (T), the antiferromagnetic orthorhombic (O) and the non-magnetic collapsed tetragonal (cT) phases of CaFe2As2. We find no evidence of additional structures for pressures up to 2.5 GPa (at 300 K). Both the T-cT and O-cT transitions exhibit significant hysteresis effects and we demonstrate that coexistence of the O and cT phases can occur if a non-hydrostatic component of pressure is present. Measurements of the magnetic diffraction peaks show no change in the magnetic structure or ordered moment as a function of pressure in the O phase and we find no evidence of magnetic ordering in the cT phase. Band structure calculations show that the transition results in a strong decrease of the iron 3d density of states at the Fermi energy, consistent with a loss of the magnetic moment.Comment: List of authors in metadata and typos in labeling of inset in Fig. 1(a) corrected. One ref. added. No other change

Solution of the Kwiecinski evolution equations for unintegrated parton distributions using the Mellin transform

The Kwiecinski equations for the QCD evolution of the unintegrated parton distributions in the transverse-coordinate space (b) are analyzed with the help of the Mellin-transform method. The equations are solved numerically in the general case, as well as in a small-b expansion which converges fast for b Lambda_QCD sufficiently small. We also discuss the asymptotic limit of large bQ and show that the distributions generated by the evolution decrease with b according to a power law. Numerical results are presented for the pion distributions with a simple valence-like initial condition at the low scale, following from chiral large-N_c quark models. We use two models: the Spectral Quark Model and the Nambu--Jona-Lasinio model. Formal aspects of the equations, such as the analytic form of the b-dependent anomalous dimensions, their analytic structure, as well as the limits of unintegrated parton densities at x -> 0, x -> 1, and at large b, are discussed in detail. The effect of spreading of the transverse momentum with the increasing scale is confirmed, with growing asymptotically as Q^2 alpha(Q^2). Approximate formulas for for each parton species is given, which may be used in practical applications.Comment: 18 pages, 6 figures, RevTe