Mobile phase composition remains the major experimental parameter influencing the separation process in reversed-phase high-performance liquid chromatography (RP-HPLC). Its influence on the retention of solutes is explained by the Hildebrand solubility parameter and solvophobic theory, which also considers molecular characteristics of the participants in a separation process. The main empirical dependences (linear and polynomial) between the retention factor and the composition of mobile phase (retention function) are discussed taking into consideration a wide range of mobile phase compositions. Two direct chromatographic indices are resulting from these equations: the extrapolated value of retention factor for zero organic content in mobile phase composition (log kw) and the solvent strength parameter (S), which for a linear retention function is its slope being constant over the entire mobile phase compositions. Another chromatographic index could result from the retention function for zero content of water in mobile phase, but this situation can be applied only for very hydrophobic solutes. For large domains of mobile phase composition, the retention function cannot be described by a single type of dependence. This explains the paradox of generating by extrapolation different values for different organic components. For the mobile phase close to pure water the retention function is different from that at average water concentration.
Mass spectrometry is crucial for analysing physicochemical and sensory properties, including colour, astringency, taste, and flavour, predicting ageing characteristics, and addressing stability issues in wine. Polyphenols are key chemical constituents in wine that are associated with health benefits and improve circulatory conditions. Advances in mass spectrometry ionisation techniques such as matrix-assisted laser desorption and ionisation and direct analysis in real-time offer high sensitivity for identifying important polyphenolic constituents in wine. High-resolution mass spectrometry, in combination with liquid chromatography, accurately identify and quantify polyphenolic compounds, even at low concentrations, and provides the possibility for further retrospective analysis and non-targeted analysis using statistical methods of data analysis. Ambient mass spectrometry techniques such as paper spray and low-temperature plasma allow solventless analysis, determining the geographical origin, authentication, and quality control of wine samples. This review will explore the potential benefits of using mass spectrometry to identify various polyphenols and polymeric polyphenols in wine, as well as recent developments and applications. Additionally, we will discuss determining antioxidant activity and total polyphenol content in wine.