The solvent strength parameter (slope) and intercept (log k w ) of the linear solvent strength model are determined for methanol-water (17 columns), acetonitrile-water (15 columns), acetone-water (7 columns), tetrahydrofuran-water (6 columns), and 2-propanol-water (4 columns) for varied compounds. It is shown that the linear region of the plots of the retention factor (log k) against the volume fraction of organic solvent (f) is largely a system property independent of solute type for compounds with accessible retention factors. Solvent strength parameters for methanol 3.12, acetonitrile 2.78, acetone 2.71, and tetrahydrofuran 2.95 are assigned for siloxane-bonded silica and porous graphitic carbon columns as an average of the compound-specific experimental values. Statistical analysis indicates that the compound-specific solvent strength parameters are column dependent and limited as a general solvent property. Evaluation of the column-specific solvent strength parameters provides further evidence that the average solvent strength parameter is column dependent. The column-specific solvent strength values are compared with the hypothetical water-organic solvent distribution systems using the system constants of the solvation parameter models as variables to confirming the column dependence of the solvent strength parameter. The column-specific solvent strength parameters can be predicted by the solvation parameter model with a typical deviation of about 0.12 over a range of 1.69 to 6.33 for the experimentally determined values. The intercept of the linear solvent strength model is shown to be both column and organic solvent dependent. Compound column-specific values are adequately described by the solvation parameter model. Log k w cannot be recommended as a descriptor of solute properties since it has no clear connection to a real distribution system.
In this article, a comparison of ionization techniques is provided and discussed. Conventional liquid chromatography with an electrospray ionization source shows higher robustness and repeatability in comparison with liquid chromatography coupled with a coordination ion spray (CIS-MS) source using silver nitrate as the dopant. However, the higher sensitivity and possibility to collect more data in untargeted applications mean CIS-MS is emerging as an instrument used in specific applications. During this research, the limit of detection (LOD) for GHRP-2 and GHRP-6 was established at 0.2 ng/mL, and the lower limit of quantification (LLOQ) was 0.5 ng/mL for CIS-MS. For conventional ESI-MS combined with solid-phase extraction on weak cation exchange columns, the limit of detection was found to be 1 ng/mL, and the lower limit of quantification was 2 ng/mL.
Dopamine, adrenaline and octopamine are small polar molecules that play a vital role in regulatory systems. In this paper, phthalylglycyl chloride was proposed as a derivatization agent for octopamine, adrenaline and dopamine determination in urine for the first time. The derivatization procedure facilitated the use of reversed-phase liquid chromatography with positive electrospray ionization–high-resolution mass spectrometry. An LC-HRMS method was developed that provided quantification limits of 5 ng/mL and detection limits of 1.5 ng/mL for all analytes. The 95–97% yield of derivates was observed after a 10 min derivatization with phthalylglycyl chloride at pH 6.5 and 30 °C. The proposed method was successfully applied to the analysis of human urine samples. The obtained results were compared with those of conventional derivatization procedures with 9-fluorenyl-methoxycarbonyl chloride and dansyl chloride.
System maps for the individual system constant of the solvation parameter model and five binary solvent containing 20-70% (v/v) acetonitrile, acetone, methanol, 2-propanol, and tetrahydrofuran on a single octadecylsiloxane-bonded silica column (Luna C18) are used to provide insight into the variation of system properties with mobile phase composition and solvent type. Selectivity differences are dominated by variation in solute size and hydrogen-bond basicity with solvent-dependent variation in dipole-type and hydrogen-bond acid interactions. Interactions involving lone pair electrons are important only in the case of the alcohols and to a lesser extent tetrahydrofuran. Selectivity differences are also dependent on solvent strength. To expand the selectivity space four ternary solvent systems (acetonitrile-methanol-water, acetonitrile-2-propanol-water, methanol-tetrahydrofuran-water, and tetrahydrofuran-2-propanol-water) 1:1:2% (v/v) containing 50% (v/v) total organic solvent are compared with the binary solvent systems at the same organic solvent composition. There is no simple model that links the system properties of the ternary solvents to the binary solvent systems, but it is demonstrated that the ternary solvent systems expand the selectivity space available for reversed-phase separations. The solvation properties of the bulk organic solvents provide insufficient information to predict selectivity in RPLC because of the dominant contribution of water and effects related to the selective solvation of the stationary phase and possible changes in the solvent-dependent microstructure of the mobile phase.