Retention prediction of analytes in reversed-phase high-performance liquid chromatography based on molecular structure

Smith, Roger M.; Burr, Christina M.

doi:10.1016/s0021-9673(01)96754-8

Cited by 39 publications

(10 citation statements)

References 7 publications

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“…The various functional groups added to the triacylglycerol molecule, however, did not constitute totally independent contributions to the retention time, and therefore the calculated incremental elution factors differ slightly from the simple sums of the individual contributions. The functional groups apparently interacted with neighboring groups (30), and this interaction altered their polarity. Thus, for triacylglycerols containing two hydroperoxy groups, the elution factors showed a 7-9% reduction from the total sum of the elution factors estimated for monohydroperoxides, depending on the exact location of the substituents.…”

Section: Resultsmentioning

confidence: 99%

Elution factors of synthetic oxotriacylglycerols as an aid in identification of peroxidized natural triacylglycerols by reverse‐phase high‐performance liquid chromatography with electrospray mass spectrometry

Sjövall

Kuksis

Marai

et al. 1997

Lipids

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Selected elution factors were determined for model oxotriacylglycerols as an aid in identification of the peroxidation products of natural triacylglycerols by reverse-phase high-performance liquid chromatography (HPLC) with electrospray mass spectrometry (LC/ES/MS). For this purpose synthetic triacylglycerols of known structure were converted to hydroperoxides, hydroxides, epoxides, and core aldehydes and their dinitrophenylhydrazones by published procedures. The oxotriacylglycerols were resolved by normal-phase thin-layer chromatography and reverse-phase HPLC, and the identities of the oxotriacylglycerols confirmed by LC/ES/MS. Elution factors of oxotriacylglycerols were determined in relation to a homologous series of saturated triacylglycerols, ranging from 24 to 54 acyl carbons, and analyzed by reverse-phase HPLC, using a gradient of 20-80% isopropanol in methanol as eluting solvent and an evaporative light-scattering detector. It was shown that the elution times varied with the nature of the functional group and its regiolocation in the triacylglycerol molecule. A total of 31 incremental elution factors were calculated from chromatography of 33 oxygenated and nonoxygenated triacylglycerol species, ranging in carbon number from 36 to 54 and in double-bond number from 0 to 6.

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Section: Resultsmentioning

confidence: 99%

Elution factors of synthetic oxotriacylglycerols as an aid in identification of peroxidized natural triacylglycerols by reverse‐phase high‐performance liquid chromatography with electrospray mass spectrometry

Sjövall

Kuksis

Marai

et al. 1997

Lipids

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“…Therefore, a reference chromatographic system to refer p values obtained in different column/mobile phase arrangements was established . This reference data set was selected from the retention measurements of Smith and Burr in a Spherisorb ODS-2 column and acetonitrile/water mobile phases. − Thus, a wide database of more than 200 compounds of a different nature is now available. , Equation 1 and the described polarity parameters have demonstrated to be able to transfer successfully retention data between solvent systems and between columns …”

Section: Introductionmentioning

confidence: 99%

A QSPR Study of the p Solute Polarity Parameter to Estimate Retention in HPLC

Bosque¹,

Sales²,

Bosch³

et al. 2003

J. Chem. Inf. Comput. Sci.

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A Quantitative Structure-Property Relationship (QSPR) model is developed to calculate the solute polarity parameter p of a set of 233 compounds of a very different chemical nature. The proposed model, derived from multiple linear regression, contains four descriptors calculated from the molecular structure and the well-known hydrophobicity parameter log P(o/w). According to the statistics obtained with the prediction set, the model has a very good prediction capacity (R(2) = 0.954, F = 889, n = 45, and SD = 0.27). The study shows that log P(o/w) and hydrogen bond acidity of the solutes are the most relevant descriptors to predict p values. This p parameter is embodied in a general equation to predict retention in reversed-phase liquid chromatography (RP-HPLC). It describes analyte retention exclusively on the basis of mobile phase/analyte/stationary phase polar interactions. Equations and procedures to determine polarity of both chromatographic phases had been successfully developed previously. Therefore, the proposed QSPR model for p estimation becomes a very useful tool in RP-HPLC optimization of procedures and methods in the everyday analytical work.

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“…In order for this approach to be useful as a method for predicting the variation of solute retention as a function of the percent ACN, it must be able to predict log k values for solutes whose retention data were not used in the derivation of UNIFAC-derived S and log k s/w values. To test this, predicted log k values for six solutes whose retention data were not used in the derivation of best-fit log k s/w values are plotted against experimental values − in Figure . While the number of data used for comparison is small, the agreement is on the whole satisfactory and shows that the method can be extended to solutes not in the training set.…”

Section: Resultsmentioning

confidence: 99%

Solvent Strength Parameters and Retention Factors in Pure Water Using UNIFAC-Predicted Activity Coefficients

Park

Jung

Vitha

et al. 2003

Ind. Eng. Chem. Res.

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It is well-known in reversed-phase liquid chromatography that the solute retention factor (k) in binary eluents is well modeled as a quasi-linear function of the eluent composition (Φ) by the equation log k ) log k s/w -SΦ, where the solute parameters k s/w and S are the retention factor in pure water and the solvent strength parameter, respectively, and Φ is the volume fraction of the organic component of the eluent. S is related to the free energy of the solute transfer from water to bulk organic liquid, which in turn is related to the infinite-dilution activity coefficients (γ ∞ ) of the solute in water and bulk organic liquid. We report that the γ ∞ values obtained from a γ ∞ prediction model, UNIFAC, can be used to predict S directly and also to aid in the determination of best-fit k s/w values for acetonitrile-water mobile-phase systems. More specifically, UNIFAC-based S values combined with experimentally determined k s/w values for a limited set of solutes can be used to predict the variations in retention as a function of mobile-phase composition in acetonitrile-water systems within the calibration range for solutes that were not in the original data set.

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Retention prediction of analytes in reversed-phase high-performance liquid chromatography based on molecular structure

Cited by 39 publications

References 7 publications

Elution factors of synthetic oxotriacylglycerols as an aid in identification of peroxidized natural triacylglycerols by reverse‐phase high‐performance liquid chromatography with electrospray mass spectrometry

Elution factors of synthetic oxotriacylglycerols as an aid in identification of peroxidized natural triacylglycerols by reverse‐phase high‐performance liquid chromatography with electrospray mass spectrometry

A QSPR Study of the p Solute Polarity Parameter to Estimate Retention in HPLC

Solvent Strength Parameters and Retention Factors in Pure Water Using UNIFAC-Predicted Activity Coefficients

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