Influence of the acid-base ionization of drugs in their retention in reversed-phase liquid chromatography

Soriano-Meseguer, Sara; Fuguet, Elisabet; Port, Adriana; Rosés, Martı́

doi:10.1016/j.aca.2019.05.063

Cited by 10 publications

(17 citation statements)

References 45 publications

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“…Vsolvent is often considered an estimation of the hold-up volume (or void volume), which corresponds to the volume of flowing eluent inside the column (VM). Although the volume of solvent measured by pycnometry can be a good estimation of VM for RPLC [29], where water and the organic solvent behave simply as the MPs and the bonded phase as the SP, this may be not especially right for HILIC. In HILIC conditions Vsolvent will include the volume of the mobile phase (VM) and the volume of the adsorbed water-rich layers acting as labile stationary phase.…”

Section: In 2008 Mccalley and Neuementioning

confidence: 99%

HILIC characterization: Estimation of phase volumes and composition for a zwitterionic column

Redón

Subirats

Rosés

2020

Analytica Chimica Acta

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A methodology for the estimation of the different phase volumes in HILIC is presented. For a ZIC-HILIC column the mobile phase volume (hold-up volume) is determined in several acetonitrile-and methanol-water compositions by a Linear Free Energy Relationships (LFER) homologous series approach involving n-alkyl-benzenes, -phenones, and -ketones. We demonstrate that the column works as a HILIC column when the mobile phase contains high and medium proportions of methanol or acetonitrile. However, for acetonitrile contents below 20%, or 40% for methanol, same column works in RPLC. In between, a mixed HILIC-RPLC behavior is observed, and solutes of low molecular volume are retained as in HILIC mode, but the largest ones show RPLC retention. From the homologous series retention data and pycnometric measurements involving the pure organic solvents and their mixtures with water, the mean solvent composition of the water-rich transition layers between column functionalization and the bulk mobile phase, which act as stationary phase, is estimated. Finally, the phase ratio between stationary and mobile phases is also estimated for each eluent composition, allowing the calculation of the corresponding stationary phase volumes. All volumes are strongly dependent on the water content in the eluent, especially when acetonitrile is selected as mobile phase constituent. In HILIC mode, when the water content in the hydroorganic mobile phase increases, the volumes of mobile phase decrease, but the volumes of stationary phase (mainly the water layer adsorbed onto the bonded-phase and the water-enriched interface) increase. However, at high water concentrations, where the column works in RPLC mode, the mobile phase volume increases and the stationary phase (which is now the bonded zwitterion) decrease when increasing the water percentage in the mobile phase.

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Section: In 2008 Mccalley and Neuementioning

confidence: 99%

HILIC characterization: Estimation of phase volumes and composition for a zwitterionic column

Redón

Subirats

Rosés

2020

Analytica Chimica Acta

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“…However, based on their PKa values in addition to their log P, the sequence would be DEXP, OSTP, DEX, DAC, and finally REM. This is due to the fact that ionizable compounds have significantly shorter retention times than unionizable compounds in reversed-phase high-performance liquid chromatography 49 .…”

Section: Resultsmentioning

confidence: 99%

“…Prediction of the drugs' order of separation. The compounds' log P (log Kow) and pka values influence their separation order 49 . OSTP, DEX, or its phosphate salt (DEXP), REM, and DAC were the drugs under investigation.…”

Section: Resultsmentioning

confidence: 99%

Development of UPLC method for simultaneous assay of some COVID-19 drugs utilizing novel instrumental standard addition and factorial design

EL-Shorbagy

Mohamed

El‐Gindy

et al. 2023

Sci Rep

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A green, rapid, and simple RP-UPLC method was developed and optimized by full factorial design for the simultaneous separation of oseltamivir phosphate, daclatasivir dihydrochloride, and remdesivir, with dexamethasone as a co-administered drug. The separation was established on a UPLC column BEH C18 1.7 µm (2.1 × 100.0 mm) connected with a UPLC pre-column BEH 1.7 µm (2.1 × 5.0 mm) at 25 °C with an injection volume of 10 µL. The detector (PDA) was set at 239 nm. The mobile phase consisted of methanol and ammonium acetate (8.1818 mM) in a ratio of 75.7: 24.3 (v/v). The flow rate was set at 0.048 mL min−1. The overall separation time was 9.5 min. The retention times of oseltamivir phosphate, dexamethasone, daclatasivir dihydrochloride, and remdesivir were 6.323 ± 0.145, 7.166 ± 0.036, 8.078 ± 0.124, and 8.572 ± 0.166 min (eight replicates), respectively. The proposed method demonstrated linearity in the ranges of 10.0–500.0 (ng mL−1) and 0.5–30.0 (µg mL−1) for oseltamivir phosphate, 50.0–5000.0 (ng mL−1) for dexamethasone, 25.0–1000.0 (ng mL−1) and 0.5–25.0 (µg mL−1) for daclatasvir dihydrochlorde, and 10.0–500.0 (ng mL−1) and 0.5–30.0 (µg mL−1) for remdesivir. The coefficients of determination (R2) were greater than 0.9999, with percentage recoveries greater than 99.5% for each drug. The limits of quantitation were 6.4, 1.8, 7.8, and 1.6 ng mL−1, and the limits of detection were 1.9, 0.5, 2.0, and 0.5 ng mL−1 for oseltamivir phosphate, dexamethasone, daclatasivir dihydrochloride, and remdesivir, respectively. The proposed method was highly precise, as indicated by the low percentage of relative standard deviation values of less than 1.2% for each drug. The average content and uniformity of dosage units in the studied drugs' dosage forms were determined. The average contents of oseltamivir phosphate, dexamethasone, daclatasivir dihydrochloride, and remdesivir were nearly 93%, 102%, 99%, and 95%, respectively, while the uniformity of dosage unit values were nearly 92%, 102%, 101%, and 97%. Two novel methods were established in this work. The first method was used to assess the stability of standard solutions. This novel method was based on the slope of regression equations. The second was to evaluate the excipient's interference using an innovative instrumental standard addition method. The novel instrumental standard addition method was performed using the UPLC instrument program. It was more accurate, sensitive, time-saving, economical, and eco-friendly than the classic standard addition method. The results showed that the proposed method can estimate the tested drugs' concentrations without interference from their dosage form excipients. According to the Eco-score (more than 75), the Green Analytical Procedure Index (GAPI), and the AGREE criteria (total score of 0.77), the suggested method was considered eco-friendly.

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“…[54, 55], Espinoza et al. [56, 57], and others [58–61]. Since the HILIC mobile phases include high concentrations of ACN, the calculated analyte charges may be significantly different than those in an aqueous environment.…”

Section: Resultsmentioning

confidence: 99%

“…The limitation of the above-described approach is that mobile phase pH and pK a values of analytes shift in presence of organic solvents; this can alter the apparent analytes' charge. This phenomenon has been studied by Wiczling et al [52,53], Bosch et al [54,55], Espinoza et al [56,57], and others [58][59][60][61]. Since the HILIC mobile phases include high concentrations of ACN, the calculated analyte charges may be significantly different than those in an aqueous environment.…”

Section: Effect Of Acn On Analyte Chargementioning

confidence: 99%

Contribution of ionic interactions to stationary phase selectivity in hydrophilic interaction chromatography

Gilár

Berthelette

Walter

2022

J of Separation Science

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We compared the separation selectivities of 19 different hydrophilic interaction chromatography columns. The stationary phases included underivatized silica and hybrid particles, cyano-bonded silica, materials with neutral ligands such as amide, diol, pentahydroxy, and urea, zwitterionic sorbents, and mixed-mode materials with amine functionalities. A set of 77 small molecules was used to evaluate the columns. We visualized the retention behavior of the different columns using retention time correlation plots. The analytes were classified as cations, anions, or neutral based on their estimated charge under the separation conditions. This involved adjusting the dissociation constants of the analytes for the acetonitrile content of the mobile phase and experimentally determining the pH of the mobile phase containing 70% acetonitrile. The retention correlation plots show that the selectivity differences strongly depended on ionic interactions. Comparisons of the neutral stationary phases (e.g., diol vs. amide) showed more similar selectivity than did comparisons of neutral columns versus columns with cation or anion exchange activity (bare silica or amine columns, respectively). The zwitterionic columns did not behave as perfectly neutral. The correlation plots indicated that they exhibited either cation or anion exchange activity, although to a lesser degree than the silica and amine-containing stationary phases.

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Influence of the acid-base ionization of drugs in their retention in reversed-phase liquid chromatography

Cited by 10 publications

References 45 publications

HILIC characterization: Estimation of phase volumes and composition for a zwitterionic column

HILIC characterization: Estimation of phase volumes and composition for a zwitterionic column

Development of UPLC method for simultaneous assay of some COVID-19 drugs utilizing novel instrumental standard addition and factorial design

Contribution of ionic interactions to stationary phase selectivity in hydrophilic interaction chromatography

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