Van't Hoff analysis in chiral chromatography

Аснин, Леонид; Stepanova, Maria V.

doi:10.1002/jssc.201701264

Cited by 76 publications

(48 citation statements)

References 108 publications

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“…Temperature is of great importance both for the optimization of enantioseparation and the elucidation of the enantiorecognition mechanisms . To eliminate the phase ratio influence, modified van't Hoff equation was undertaken to investigate the chiral discrimination process of the two enantiomers :

\ln α = - Δ Δ H^{0} / R T + Δ Δ S^{0} / R

Where R is the universal gas constant (8.314 J/ (mol K)), T is the absolute temperature.…”

Section: Resultsmentioning

confidence: 99%

Efficient preparative separation of 6‐(4‐aminophenyl)‐5‐methyl‐4, 5‐dihydro‐3(2H)‐pyridazinone enantiomers on polysaccharide‐based stationary phases in polar organic solvent chromatography and supercritical fluid chromatography

Cheng

Cai

et al. 2019

J of Separation Science

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6-(4-Aminophenyl)-5-methyl-4,5-dihydro-3(2H)-pyridazinone is a key synthetic intermediate for cardiotonic agent levosimendan. Very few studies address the use of chiral stationary phases in chromatography for the enantioseparation of this intermediate. This study presents two efficient preparative methods for the isolation of (R)(−)-6-(4-aminophenyl)-5-methyl-4,5-dihydro-3(2H)-pyridazinone in polar organic solvent chromatography and supercritical fluid chromatography using polysaccharide-based chiral stationary phases and volatile organic mobile phases without additives in isocratic mode. Under optimum conditions, Chiralcel OJ column showed the best performance (α = 1.71, Rs = 5.47) in polar organic solvent chromatography, while Chiralpak AS column exhibited remarkable separations (α = 1.81 and Rs = 6.51) in supercritical fluid chromatography with an opposite enantiomer elution order. Considering the sample solubility, runtime and solvent cost, the preparations were carried out on Chiralcel OJ column and Chiralpak AS column (250 × 20 mm i.d.; 10 μm) in polar organic mode and supercritical fluid chromatography mode with methanol and CO 2 /methanol as mobile phases, respectively. By utilizing the advantages of chromatographic techniques and polysaccharide-based chiral stationary phases, this work provides two methods for the fast and economic preparation of (R)(−)-6-(4-aminophenyl)-5-methyl-4,5-dihydro-3(2H)-pyridazinone, which are suitable for the pharmaceutical industry. K E Y W O R D S chiral separation, enantiomers, levosimendan, polar organic solvent chromatography, supercritical fluid chromatography 2482

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\ln α = - Δ Δ H^{0} / R T + Δ Δ S^{0} / R

Where R is the universal gas constant (8.314 J/ (mol K)), T is the absolute temperature.…”

Section: Resultsmentioning

confidence: 99%

Efficient preparative separation of 6‐(4‐aminophenyl)‐5‐methyl‐4, 5‐dihydro‐3(2H)‐pyridazinone enantiomers on polysaccharide‐based stationary phases in polar organic solvent chromatography and supercritical fluid chromatography

Cheng

Cai

et al. 2019

J of Separation Science

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show abstract

“…The nature of analyte/CSP association can be explored on the basis of thermodynamic considerations. Theory of adsorption phenomena in chromatography, and methods for profiling temperature dependence of retention and selectivity and calculating thermodynamic quantities associated with the adsorption of analytes on the CSP surface have been the matter of several papers [13,14,[35][36][37][38][39][40].…”

Section: Effect Of Temperature On the Enantioseparation With Coated Amentioning

confidence: 99%

Comparative enantioseparation of chiral 4,4’-bipyridine derivatives on coated and immobilized amylose-based chiral stationary phases

Peluso

Sechi

Lai

et al. 2020

Journal of Chromatography A

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The chromatographic performances of four coated and immobilized amylose phenylcarbamate-based chiral columns were evaluated and compared under normal phase (NP) elution conditions by using chiral 4,4'-bipyridine derivatives as analytes. n-Hexane/2-propanol 90:10 and n-hexane/2-propanol/methanol 90:5:5 mixtures were employed as mobile phases (MPs), and the effect of adding methanol in the MP on retention and selectivity was considered. The effect of temperature on retention and selectivity was also evaluated, and overall thermodynamic parameters associated with the analyte adsorption onto the CSP surface were derived from van't Hoff plots. Interesting cases of enantiomer elution order (EEO) reversal, which are dependent on the nature of polar modifier, analyte structure, column-type, and temperature, were observed. The impact of substitution pattern and electronic properties of analytes and selectors on the separation behaviour was investigated by correlating chromatographic parameters and molecular properties determined by using density functional theory (DFT) calculations. Both coated and immobilized amylose tris(3,5-dimethylphenylcarbamate) columns allowed for the baseline enantioseparation (2.0 ≤ R S ≤ 4.9) of all 4,4'-bipyridines considered in this study. These results appear particularly useful because both enantiomers of these 4,4'-bipyridine derivatives are currently under investigation as new inhibitors of transthyretin fibrillogenesis, a biochemical phenomenon which is implicated to cause amyloid diseases.

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“…There is a longstanding debate in the literature regarding the physical basis of the so-called enthalpy-entropy compensation (EEC), which is observed in a wide range of fields in chemistry; [1][2][3][4][5][6][7][8] biology [9][10][11][12][13][14][15] and solid-state physics: [16][17][18][19] EEC describes a linear relation between two thermodynamic parameters, the enthalpy~H and entropy~S, of a series of similar reactions. Examples include the denaturation of closely related proteins, reactions in slightly varying solvents, or reactions of hydrogen with metal alloys.…”

Section: Introductionmentioning

confidence: 99%

Single Quality Factor for Enthalpy‐Entropy Compensation, Isoequilibrium and Isokinetic Relationships

et al. 2020

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Enthalpy‐entropy compensation (EEC) is very often encountered in chemistry, biology and physics. Its origin is widely discussed since it would allow, for example, a very accurate tuning of the thermodynamic properties as a function of the reactants. However, EEC is often discarded as a statistical artefact, especially when only a limited temperature range is considered. We show that the likeliness of a statistical origin of an EEC can be established with a compensation quality factor (CQF) that depends only on the measured enthalpies and entropies and the experimental temperature range. This is directly derived from a comparison of the CQF with threshold values obtained from a large number of simulations with randomly generated Van ‘t Hoff plots. The value of CQF is furthermore a direct measure of the existence of a genuine isoequilibrium or isokinetic relationship.

show abstract

Van't Hoff analysis in chiral chromatography

Cited by 76 publications

References 108 publications

Efficient preparative separation of 6‐(4‐aminophenyl)‐5‐methyl‐4, 5‐dihydro‐3(2H)‐pyridazinone enantiomers on polysaccharide‐based stationary phases in polar organic solvent chromatography and supercritical fluid chromatography

Efficient preparative separation of 6‐(4‐aminophenyl)‐5‐methyl‐4, 5‐dihydro‐3(2H)‐pyridazinone enantiomers on polysaccharide‐based stationary phases in polar organic solvent chromatography and supercritical fluid chromatography

Comparative enantioseparation of chiral 4,4’-bipyridine derivatives on coated and immobilized amylose-based chiral stationary phases

Single Quality Factor for Enthalpy‐Entropy Compensation, Isoequilibrium and Isokinetic Relationships

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