RESUMO
Weak-acid anions such as borate and cyanide, present problems in chemically suppressed ion chromatography, since the acids are weakly ionised, giving low conductivity and therefore decreased sensitivity. For borate this problem was overcome by converting the weak acid to its sodium salt, by the use of a second anion micromembrane suppressor (AMMS) as an ion exchange reactor (IER), flushed by EDTA reagent, to supply sodium ions for the conversion. This paper will discuss the use of this IER system to determine cyanide, which is also a very weak acid, with a similar pKa to borate. The detection limit for cyanide of 50 microM compare favourably with indirect conductivity detection.
Assuntos
Cromatografia por Troca Iônica/métodos , Condutometria/métodos , Cianetos/análiseRESUMO
Anions of weak acids can represent a problem when determined via chemically suppressed ion chromatography as the acids can be weakly ionised, giving low conductivity and hence low sensitivity. Previous work showed that converting some weak acids back to their sodium salts, using a second micromembrane suppressor, greatly enhanced conductivity and thus sensitivity. This paper will discuss further work in optimising the conversion for boric acid by using sodium salts of EDTA and the mechanisms involved.
Assuntos
Ácidos/análise , Cromatografia por Troca Iônica/métodos , Boratos/análise , Ácidos Bóricos/análise , Condutometria/métodos , Ácido Edético/química , Concentração de Íons de Hidrogênio , Modelos QuímicosRESUMO
Previously we demonstrated that the conductometric determination of anions of weak acids in chemically suppressed ion chromatography could be enhanced, by conversion of the acid to a conjugate salt, if the anion was present above what we termed the critical point concentration (CPC). In this paper we have developed a simple theoretical model for the calculation of CPCs for weak acid/conjugate salt pairs. The CPC was found to be dependent on the acid ionization constant K(a) and the molar ionic conductivities (MICs) of the ions present. For monovalent anions with a MIC in the common range 25-75 S cm(2) mol(-)(1), with sodium or potassium as cations, the CPCs could be estimated from the expression pC ≈ pK(a) - 1, where pC = -log CPC. For formate, benzoate, and acetate, excellent agreement was found between the calculated and experimental CPCs, with a mean deviation of 0.05 mM. For fluoride, the calculated and experimental CPCs were 7.4 and 9.2 mM, respectively. Experimental CPCs could not be determined for other anions as their calculated CPCs were below the detection limits of the IC system. The simple theoretical model could also be used to estimate the expected conductivity enhancement for the conversion of weak acid to a particular conjugate salt. The effects of detector linearity and dispersion in the IC system on the use of CPCs are also discussed.
RESUMO
A capillary electrophoresis (CE) investigation of the enantiomeric separation of propranolol and some of its metabolites using CE was undertaken. Resolution of the enantiomers was achieved using hydroxypropyl-beta-cyclodextrin (HP-beta-CD) as the chiral selector. Parameters found to influence separation include cyclodextrin concentration, potential, pH and organic solvent/additive. It was observed that 17 mM HP-beta-CD gave optimum separation over the concentration range used in this study, however different racemates appear to have best resolution at different CD concentration. The potential does not have a great effect on enantiomer resolution, but appears to cause relative metabolite migration times to alter such that separation is affected. Carrier pH affects both migration time, and enantiomer resolution and metabolite separation. Above pH 5 inferior results are obtained. This is the first report of enantiomeric resolution of propranolol metabolites using CE.
Assuntos
Ciclodextrinas/metabolismo , Eletroforese Capilar/métodos , Propranolol/isolamento & purificação , Sequência de Carboidratos , Concentração de Íons de Hidrogênio , Isomerismo , Metanol/farmacologia , Dados de Sequência Molecular , Estrutura Molecular , Propranolol/análogos & derivados , Propranolol/metabolismo , SolventesRESUMO
DF-2 is a recently described gram-negative bacillus known to be part of the normal flora of dogs. A variety of serious infections (bacteremia, endocarditis, meningitis, cellulitis) caused by DF-2 have occurred following dog bites. Asplenic patients appear to be especially susceptible to DF-2 infection. Two cases of DF-2 bacteremia occurring after domestic cat bites are reported. Sepsis and meningitis developed in an asplenic patient, and an immunocompetent patient presented with primary cellulitis. Both patients responded promptly to parenteral antibiotic therapy. DF-2 must now be considered along with Pasteurella multocida in the differential of cellulitis or sepsis following bites or scratches from domestic cats.