Adsorption behavior of hexafluorophosphate on selected bonded phases.

The adsorption behavior of ammonium hexafluorophosphate was studied on four HPLC columns packed with adsorbents of different ability for dispersive interactions using frontal chromatography with LC/MS detection in negative ESI mode. Hexafluorophosphate (PF(6)(-)) adsorption isotherms were measured from acetonitrile/water and methanol/water mixtures. Increased PF(6)(-) adsorption with increased acetonitrile content was found between 0 and 15% of acetonitrile in the eluent. Further increase of the acetonitrile concentration leads to an exponential decrease of PF(6)(-) adsorption. Methanol, on the other hand, causes a steady decrease of PF(6)(-) adsorption with increased organic concentration in the mobile phase.

Solid-phase micro-extraction of drugs from biological matrices.

Solid phase micro-extraction was originally designed as a technique for the solvent-free analysis of volatile organic contaminants in environmental samples. However, a wide variety of applications are now being pursued, including the analysis of drugs from a variety of matrices. In this review, the analysis of drugs by SPME from biological and related matrices, including water, urine, blood, hair and saliva, is discussed. A general overview of the special problems and techniques involved in SPME from biological matrices is presented, along with specific references and discussion of the analysis of many types of drugs and metabolites. It is seen that SPME is a highly versatile and flexible technique for these analyses.

Characterization of inclusion complexes of betamethasone-related steroids with cyclodextrins using high-performance liquid chromatography.

HPLC was used to study the inclusion complexes formed between various beta- and gamma-cyclodextrins and a series of corticosteroids related to betamethasone. Apparent association constants were measured in acetonitrile-water for a set of 13 steroids. An increase in the stability of the steroid-cyclodextrin complex is observed at lower concentrations of acetonitrile. The effects of the nature of the halide at the 9-position, the location of a double bond within the C-ring, substitution at the 9- and 11-positions, and modification of the D-ring of the steroid backbone were studied. The 11- and 17-positions were found to be critically involved in the inclusion process. Larger apparent association constants were obtained with gamma-cyclodextrin (gamma-CD) than with beta-cyclodextrin (beta-CD) due to the increased diameter of the gamma-CD cavity. Van't Hoff plots were constructed to examine the thermodynamic properties of the inclusion process. Plots constructed using retention factors were found to be nonlinear when gamma-CD was present in the mobile phase. This is due to an increase in the strength of the inclusion complex as temperature decreases. Plots constructed using apparent association constants were linear, indicating that the mechanism of inclusion does not change over the range of temperatures studied (10 to 80 degrees C). Enthalpy-entropy compensation was observed for 11 of the 13 steroids studied. The usefulness of cyclodextrins to achieve the separation of steroids in HPLC is discussed and a practical application for the analysis of a steroid and three potential impurities is described.

Determination of apparent association constants of steroid-cyclodextrin inclusion complexes using a modification of the Hummel-Dreyer method.

A modified Hummel-Dreyer method was used to calculate the apparent association constants of steroid-cyclodextrin inclusion complexes. An external calibration technique was employed, using the y-intercept from a plot of peak area versus concentration to correct for sample solvent effects. Mobile phase temperature and sample diluent organic content were found to be critical factors affecting the accuracy and reproducibility of the results. For four of six sets of data, the modified Hummel-Dreyer method yielded statistically equivalent results to another HPLC method for determining apparent association constants. Limitations of the modified Hummel-Dreyer method are discussed. In particular, the accuracy of the method is poor when measuring small apparent association constants.

Modeling flavor release using inverse gas chromatography-mass spectrometry.

Inverse gas chromatography (IGC)-mass spectrometry was used to determine the extent of flavor release from a food matrix as a function of moisture uptake. At the surface of a solid, components with higher binding affinities can exchange with and replace components with lower binding affinities. As a low moisture baked product absorbs moisture from the air, flavor is lost from the matrix as water molecules exchange with the flavor molecules. The amount of flavor lost over time can be modeled using this approach to determine the onset of flavor release and total amount of flavor release as well as the identity of the released components and their relative order of exclusion from the matrix.

Novel techniques for enhancing sensitivity in static headspace extraction-gas chromatography.

Static headspace extraction-gas chromatography (SHE-GC) is one of the most commonly used techniques for the analysis of volatile compounds. It is considered by most to be a mature technique and to an extent this is true: there are many users from outside the traditional chromatography research community developing and publishing SHE-GC methods and there are numerous instruments and devices for SHE-GC commercially available. However, research on new SHE-GC methods continues. In this review, several interesting new developments in SHE-GC are described using examples from the past three years' literature. First, the fundamental theory of SHE-GC is reviewed to provide a basis and common theme for the discussion of new methods. Next, several areas of SHE-GC research are explored: new sampling configurations, analyte derivatization and ionic liquids as solvents. These are all means for enhancing partitioning of the analyte into the vapor phase, thus improving analytical sensitivity of the overall SHE-GC method. Ideally, partitioning of analytes into the vapor phase is increased while partitioning of matrix components is not, or is decreased. There are many aspects of the seemingly straightforward process in SHE-GC that require further fundamental research to extend the application range of SHE-GC and to make method development more systematic.