Linear free energy relationship models for the retention of partially ionized acid-base compounds in reversed-phase liquid chromatography

Soriano-Meseguer, Sara; Fuguet, Elisabet; Abraham, Michael H.; Port, Adriana; Rosés, Martı́

doi:10.1016/j.chroma.2020.461720

Cited by 15 publications

(3 citation statements)

References 75 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…A variation of the method derived from Linear Free Energy Relationships (LFER) models was proposed in an earlier study [ 24 ]. In the Abraham LFER model [ 25 ], the LFER variable (log k in chromatography [ 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 ]), is given as a linear combination of the solute-solvent interactions modeled by the solute descriptors accounting for dispersion forces ( E ), dipolarity/polarizability ( S ), hydrogen bond acidity ( A ), hydrogen bond basicity ( B ) and molecular volume ( V ) according to Equation (4):

where c is a non-solute dependent term accounting mainly for the chromatographic phase ratio, and e , s , a , b , and v the complimentary descriptors of the chromatographic system, all of them obtained by linear regression of the retention of a series of solutes against their solute descriptors. The Abraham descriptors E , S , A , and B for individual homologues in a series are almost constant and only V changes sequentially (linearly in fact) with the member number (number of -CH 2 - groups in the side alkyl chain).…”

Section: Resultsmentioning

confidence: 99%

Evaluation of Hold-Up Volume Determination Methods and Markers in Hydrophilic Interaction Liquid Chromatography

2023

Self Cite

View full text Add to dashboard Cite

Common methods for hold-up time and volume determination in Reversed-Phase Liquid Chromatography (RPLC) have been tested for Hydrophilic Interaction Liquid Chromatography (HILIC). A zwitterionic ZIC-HILIC column has been used for the testing. The pycnometric determination method, based on differences in column weight when filled with water or organic solvent, provides the overall volume of solvent inside the column. This includes the volume of eluent semi-sorbed on the packing of the column, which acts as the main stationary phase. The homologous series approach, based on the retention behavior of homologues in relation to their molecular volume, allows the determination of accurate hold-up volumes. However, the application of this method is time-consuming. In some cases, large neutral markers with poor dipolarity/polarizability and hydrogen bonding interactions can be used as hold-up volume markers. This is the case of dodecylbenzene and nonadecane-2-one in clearly HILIC behaving chromatographic systems, the use of decanophenone as a marker can be even extended to the boundary between HILIC and RPLC. The elution volume of the marker remains nearly unaffected by the concentration of ammonium acetate in the mobile phase up to 20 mM. The injection of pure solvents to produce minor base-line disturbance as hold-up markers is strongly discouraged, since solvent peaks are complex to interpret and depend on the ionic strength of the eluent.

show abstract

Section: Resultsmentioning

confidence: 99%

Evaluation of Hold-Up Volume Determination Methods and Markers in Hydrophilic Interaction Liquid Chromatography

2023

Self Cite

View full text Add to dashboard Cite

show abstract

“…Not least due to its simplicity, LSS theory is used frequently to predict the retention factors and the related elution times for changing mobile phase compositions [21,22 ], including within commercial software. More advanced retention models considering both mobile and stationary phase properties are the linear solvation energy relationships (LSER) introduced in the 1980s and still used [23][24][25], again including within commercial software. LSER uses semi-empirical expressions, derived from first principles, to relate the retention time to solvent-dependent solute parameters such as polarisability, hydrogen bond acidity/basicity and molecular volume.…”

Section: Retention Modelsmentioning

confidence: 99%

Recent advances in modelling and control of liquid chromatography

Besenhard

Tsatse

Mazzei

et al. 2021

Current Opinion in Chemical Engineering

View full text Add to dashboard Cite

For more than a century, chromatography has been indispensable as a separation method for both analytics and purification. Among the variety of chromatographic techniques, liquid chromatography has a special status owing to its efficiency and versatility, and its status is further enhanced by the continuous improvements of analysers, materials, methods and understanding, all supported by computational approaches. High performance liquid chromatography (HPLC) has always held a special place in pharmaceutical processing, and computational HPLC has been explored since the very early stages of computing, although without having yet reached its full potential. Herein, we provide a comprehensive and critical review of recent developments in designing and operating liquid chromatographic systems, focussing on their modelling approaches and control strategies at large scale.

show abstract

“…log 𝑘 = 𝑐 + 𝑒E + 𝑠𝑆 + 𝑎A + 𝑏B • + 𝑣V (1) According to this general form of the solvation parameter model, a particular free energy-related parameter, such as the logarithm of the retention factor (log k), is correlated to the terms describing electron lone pair interactions (e.E), dipole type interactions (s.S), hydrogen-bond acidity (a.A), hydrogen-bond basicity (b.B • ), and dispersion type interactions (v.V) [8][9][10]. Where the term c is the intercept of the model, which is a measure of the phase ratio [11].…”

Section: Introductionmentioning

confidence: 99%

Selectivity comparison of acetonitrile‐methanol‐water ternary mobile phases on an octadecylsiloxane‐bonded silica stationary phase

Atapattu

2023

J of Separation Science

View full text Add to dashboard Cite

The solvation parameter model was used in this study to investigate various intermolecular interactions that influence retention on the standard C18 stationary phase for the solvent system acetonitrile:methanol (ACN:MeOH, 1:1). In comparison to the organic mobile phase modifiers acetonitrile, acetone, methanol, 2‐propanol, and tetrahydrofuran, the solvent strength for the ACN:MeOH (1:1) solvent system was evaluated. To facilitate the interpretation of various intermolecular interactions that contribute to retention on a standard C18 stationary phase for the solvent system ACN:MeOH (1:1), system maps were constructed and compared with those of acetone, tetrahydrofuran, acetonitrile, 2‐propanol, and methanol. The solvation parameter models were constructed for the ternary solvent system ACN:MeOH (1:1)‐water, and in the models constructed, the coefficient of determination values were from 0.998 to 0.999, the Fisher statistic values for the models were from 1687 to 4015, and the standard error of the estimate values ranged from 0.022 to 0.029. The solvent system ACN:MeOH (1:1) has retention properties more similar to methanol than acetonitrile, indicating methanol's influence is more dominant.

show abstract

Linear free energy relationship models for the retention of partially ionized acid-base compounds in reversed-phase liquid chromatography

Cited by 15 publications

References 75 publications

Evaluation of Hold-Up Volume Determination Methods and Markers in Hydrophilic Interaction Liquid Chromatography

Evaluation of Hold-Up Volume Determination Methods and Markers in Hydrophilic Interaction Liquid Chromatography

Recent advances in modelling and control of liquid chromatography

Selectivity comparison of acetonitrile‐methanol‐water ternary mobile phases on an octadecylsiloxane‐bonded silica stationary phase

Contact Info

Product

Resources

About