The lipophilicity of parabens estimated on reverse phases chemically bonded and oil‐impregnated plates and calculated using different computation methods

The chromatographic behaviour of the parabens has been investigated on RP‐18F_254S, RP‐18WF_254S, CNF_254S, Diol F_254s and silica gel 60F₂₅₄ plates impregnated with different oils (paraffin, olive, sunflower and corn) using methanol–water mixtures in different volume proportions as mobile phases, the regression determination coefficients being excellent (higher than 0.98 for the majority of compounds). Moreover, highly significant correlations were obtained between different experimental indices of lipophilicity (R_M0, b and scores corresponding to the first principal component (PC1)) and computed log P values. All types of stationary phases investigated appear to be highly suited for estimating the lipophilicity of the parabens.     

Micellar liquid chromatography for lipophilicity determination of new biologically active 1,3‐purinodiones

A series of newly synthesized 1,3‐purinodiones with potential anticonvulsant activity, exhibiting affinity to adenosine A₁ and/or A_2A receptors, were subjected to micellar LC (MLC) with SDS as micelle‐forming agent and n‐propanol as organic modifier. Two C18 silica‐based columns were employed in MLC: a particle one and a monolithic. In parallel, those derivatives were also analyzed in RP‐LC on four silica‐based columns and on an immobilized artificial membrane column. The correlations between the relevant logarithms of the retention factors of analytes obtained in MLC, immobilized artificial membrane and RP‐LC systems on the one hand, and the calculated log P (clog P) and log D values (clog D) on the other, were examined. The level of the correlations of retention data from MLC and RP‐LC systems with clog P and clog D obtained is similar but it could be stressed that MLC allows increasing the speed of analysis and using only one mobile phase. Moreover, there is no need of applying an extrapolation procedure in lipophilicity determination. Therefore, the MLC systems, providing chromatographic data in a fast and efficient manner, were demonstrated as promising alternatives to the classical RP‐LC systems to estimate the lipophilicity of drugs and drug candidates.     

Unconventional TLC systems in lipophilicity determination: A review

ABSTRACT

This review focuses on four unusual thin-layer chromatography (TLC) approaches for the determination of lipophilicity: (1) the use of medium-polar stationary phases: CN, NH₂, and DIOL instead of RP plates, together with water-based mobile phase; (2) the use of silica gel in a typical normal-phase manner and treating extrapolated retention indices as the “reversed lipophilicity”; (3) the use of oil impregnated silica gel in the reversed-phase manner; and (4) the use of salting-out mobile phases. The chromatographic indices obtained in these systems are numerously reported as well correlated with lipophilicity and they are an interesting alternative to classical RP systems approaches.     

Effect of the structure and density of chemically bonded C18 phase on the recovery of tryptophan and its metabolites from human urine

A series of materials with chemically bonded C18 phase for use as the packings in clean-up columns for solid-phase extraction were prepared. The effects of the monomeric and/or polymeric structure of the chemically bonded phase and of the porous structure of the silica gel support on the recovery of tryptophan and two of its metabolites used as test substances were considered. It appeared that the best recoveries of at least 60% of the three test substances were obtained on material of the "monomer" type containing chemically bonded C18 phase characterized by a high coverage density of alpha RP approximately 3.8 mumol/m2. The use of a silica gel support with a larger pore size and volume permits not only the effective isolation of individual substances, e.g., from urine, but also their 5-fold concentration.     

Direct analysis of pharmaceutical formulations from non‐bonded reversed‐phase thin‐layer chromatography plates by desorption electrospray ionisation ion mobility mass spectrometry

The direct analysis of pharmaceutical formulations and active ingredients from non‐bonded reversed‐phase thin layer chromatography (RP‐TLC) plates by desorption electrospray ionisation (DESI) combined with ion mobility mass spectrometry (IM‐MS) is reported. The analysis of formulations containing analgesic (paracetamol), decongestant (ephedrine), opiate (codeine) and stimulant (caffeine) active pharmaceutical ingredients is described, with and without chromatographic development to separate the active ingredients from the excipient formulation. Selectivity was enhanced by combining ion mobility and mass spectrometry to characterise the desorbed gas‐phase analyte ions on the basis of mass‐to‐charge ratio (m/z) and gas‐phase ion mobility (drift time). The solvent composition of the DESI spray using a step gradient was varied to optimise the desorption of active pharmaceutical ingredients from the RP‐TLC plates. The combined RP‐TLC/DESI‐IM‐MS approach has potential as a rapid and selective technique for pharmaceutical analysis by orthogonal gas‐phase electrophoretic and mass‐to‐charge separation. Copyright © 2009 John Wiley & Sons, Ltd.     

Comprehensive evaluation of lipophilicity of biogenic amines and related compounds using different chemically bonded phases and various descriptors

The retention behavior for a series of biogenic amines and related sympathomimetic drugs has been investigated in reversed-phase thin-layer chromatography using RP-2, RP-8, RP-18W, and Diol stationary phase and mixtures of phosphate buffer (pH = 7.10) and methanol in different proportions as mobile phases. Several methodologies like arithmetic mean of experimental retention values, extrapolation to zero methanol concentration procedure and principal component analysis were applied to retention data values (R(M)) in order to determine relevant parameters (mean of R(M) - mR(M), R(M0), and scores corresponding to the first principal component - PC1/R(M) respectively) encoding information on the lipophilic behavior of compounds. High similarities in lipophilicity behavior of investigated amines were highlighted by mR(M) and PC1/R(M) lipophilicity indices for all of the studied stationary phases. The experimental results were compared with some computed lipophilicity parameters expressed as distribution coefficients at working pH (logD), partition coefficients (logP(N), logP(I), and diff(logP(N-I))) concerning both neutral and fully protonated species and difference between both species, and also with various lipophilicity values (logP) generated by different commonly used software. Significant correlations were observed between the experimental lipophilicity indices mR(M) respectively PC1/R(M) and diff(logP(N-I) ) values in all cases.     

Use of Principal Component and Cluster Analysis for the Comparison of Reversed-Phase HPLC Columns

Abstract

The retention of ethoxylated nonylhylphenyl surfactants was determined in reversed-phase high-performance liquid chromatography (RP-HPLC) using various supports (C1, C2, C6, C8, C18, polyethylene-coated silica, and polyethylene-coated alumina). The retention data matrix was evaluated both by principal component analysis and cluster analysis. The retention characteristics of both polyethylene-coated supports were similar to that of C1, the retention capacity of RP columns for surfactants increased with the increasing length of the covalently bonded hydrocarbon chain. The retention of ethoxylated surfactants depended nonlinearly on the length of ehtyleneoxide chain suggesting that the polar ethyleneoxide chains are in folded state under the chromatographic separation.     

Olive oil or lard?: Distinguishing plant oils from animal fats in the archeological record of the eastern Mediterranean using gas chromatography/combustion/isotope ratio mass spectrometry

Distinguishing animal fats from plant oils in archaeological residues is not straightforward. Characteristic plant sterols, such as β-sitosterol, are often missing in archaeological samples and specific biomarkers do not exist for most plant fats. Identification is usually based on a range of characteristics such as fatty acid ratios, all of which indicate that a plant oil may be present, none of which uniquely distinguish plant oils from other fats. Degradation and dissolution during burial alter fatty acid ratios and remove short-chain fatty acids, resulting in degraded plant oils with similar fatty acid profiles to other degraded fats. Compound-specific stable isotope analysis of δ(13)C(18:0) and δ(13)C(16:0), carried out by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS), has provided a means of distinguishing fish oils, dairy fats, ruminant and non-ruminant adipose fats, but plant oils are rarely included in these analyses. For modern plant oils where C(18:1) is abundant, δ(13)C(18:1) and δ(13)C(16:0) are usually measured. These results cannot be compared with archaeological data or data from other modern reference fats where δ(13)C(18:0) and δ(13)C(16:0) are measured, as C(18:0) and C(18:1) are formed by different processes resulting in different isotopic values. Eight samples of six modern plant oils were saponified, releasing sufficient C(18:0) to measure the isotopic values, which were plotted against δ(13)C(16:0). The isotopic values for these oils, with one exception, formed a tight cluster between ruminant and non-ruminant animal fats. This result complicates the interpretation of mixed fatty residues in geographical areas where both animal fats and plant oils were in use.     

Usefulness of chaotropic salt additive in RP‐HPLC of organic nonionized compounds

New synthesized 1,4‐disubstituted thiosemicarbazide derivatives were analyzed in the RP system, modified with the addition of salts; chaotropic (sodium hexafluorophosphate – Na PF₆), cosmotropic (sodium phosphate – NaH₂PO₄), and neutral (NaCl) on Zorbax XDB C18 column. The effect of the eluent composition on the analytes retention (k), system efficiency (N), peak symmetry (A_s), and LOD values were all examined and compared to unmodified organic‐aqueous mobile phase system. It was established that eluent modified with chaotropic salts addition was also the most advantageous according to other peak parameters such as the theoretical plates numbers and asymmetry factors. The lower LOD values were achieved in comparison to unmodified organic‐aqueous eluent system. Compatibility of lipophilicity parameters calculated by the use of computer software with experimental ones measured by RP‐HPLC was also the best for chaotropic modified mobile phase. To explain the observed phenomena, molecular modeling was performed for chosen representative compound in different environment representing examined mobile phase composition.     

Evaluation of the lipophilicity of bile acids and their derivatives by thin-layer chromatography and principal component analysis

The lipophilic character of bile acids and their glyco- and tauro-conjugates was studied. The classical R(Mo) values were measured by means of reversed thin-layer chromatography using a mixture of methanol-water as the solvent system and compared with the factors scores obtained by principal component analysis based also onto the TLC-retention data. The reliability of the factor scores values as lipophilic indices are shown by their high correlation with the classical R(Mo) values. In addition, a better correlation was observed between scores corresponding to the first principal components and the partition coefficients (log P) of bile acids. Finally, the "lipophilicity chart" described by the first two components has the effect of separating compounds from each other most effectively from the congeneric aspect point of view.     

Zeta potential determination as a new way of stationary phases characterization for liquid chromatography

A set of seven homemade octadecyl silica‐based bonded phases was investigated. Their zeta potential data in methanol and ACN as well as in methanol–water and ACN–water solution were obtained using Zetasizer. The influence of both the coverage density of bonded ligands and the end‐capping of the modified surface on these data was investigated. Presented results may give useful information about the accessibility of the residual silanols in different mobile phases during the chromatographic analysis. Those measurements may be useful to choose chemically bonded stationary phases for CEC. The results also confirm the phenomena of anion exclusion from the pores of stationary‐bonded phase.     

Comprehensive Review on Application of FTIR Spectroscopy Coupled with Chemometrics for Authentication Analysis of Fats and Oils in the Food Products

Currently, the authentication analysis of edible fats and oils is an emerging issue not only by producers but also by food industries, regulators, and consumers. The adulteration of high quality and expensive edible fats and oils as well as food products containing fats and oils with lower ones are typically motivated by economic reasons. Some analytical methods have been used for authentication analysis of food products, but some of them are complex in sampling preparation and involving sophisticated instruments. Therefore, simple and reliable methods are proposed and developed for these authentication purposes. This review highlighted the comprehensive reports on the application of infrared spectroscopy combined with chemometrics for authentication of fats and oils. New findings of this review included (1) FTIR spectroscopy combined with chemometrics, which has been used to authenticate fats and oils; (2) due to as fingerprint analytical tools, FTIR spectra have emerged as the most reported analytical techniques applied for authentication analysis of fats and oils; (3) the use of chemometrics as analytical data treatment is a must to extract the information from FTIR spectra to be understandable data. Next, the combination of FTIR spectroscopy with chemometrics must be proposed, developed, and standardized for authentication and assuring the quality of fats and oils.     

Update on solid-phase extraction for the analysis of lipid classes and related compounds

This article provides information on the different procedures and methodologies developed when solid-phase extraction (SPE) is used for lipid component separation. The analytical systematics, established by different authors and designed to separate groups of compounds and also specific components by using a combination of chromatographic supports and solvents are presented. The review has been divided into three parts, which we consider well defined: edible fats and oils, fatty foods and biological samples. Separations of non-polar and polar lipids is the most extensive systematic, although many other published methods have been established to isolate specific components or a reduced number of components from edible fats and oils, fatty foods or biological samples susceptible to further analysis by other quantitative techniques.     

Chemometrical applications in an industrial food research laboratory

Early typical chemometrical applications in oils and fats research concernedpattern recognition problems using multivariate analysis (principal component analysis, discriminant analysis, canonical variates). Various types of fish oils can now be quickly allocated with respect to their origin. Fuzzy set theory was used in a different approach to classification applied to the allocation of yellow fat spreads into product categories using sensory attributes scored on a truth scale. Partial least-squares technique has found practical applications in problems of multivariate calibration, sensory analysis and quantitative structure-activity relationships. Also the theoretical aspects of PLS regression have been investigated, in particular the underlying optimization criterion and the relation to other multivariate techniques. Mixed integer programming has been helpful in identifying and quantifying the oil composition of unknown fat blends from their fatty acid profiles, improving upon an earlier constrained regression technique using brute force all-possible subset selection.