Stochastic Theory of Chromatography: The Characteristic Function Method and the Approximation of Chromatographic Peak Shape

Dondi, Francesco; Blo, G.; Remelli, Maurizio; Reschiglian, Pierluigi

doi:10.1007/978-94-011-2686-1_6

Cited by 18 publications

(27 citation statements)

References 15 publications

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“…A possible explanation for these data is the assumption of an enantioselective recognition mechanism in which l-enantiomers do not experience selective interactions and are, accordingly, eluted at retention volumes similar to those of Gly. d-Amino acids, instead, may have enantioselective interactions at higher affinity [2,14,[37][38][39][40]42,43].…”

Section: Amino Acidsmentioning

confidence: 99%

“…For these reasons, the data presented in this work should be considered as a preliminary study. Further empirical and theoretical investigations are being planned to investigate these aspects through the use of a recently developed stochastic microscopic-molecular approach [14,[40][41][42][43]. The complexity of the subject requires a specific discussion that goes beyond the scope of this paper.…”

Section: Amino Acidsmentioning

confidence: 99%

See 1 more Smart Citation

Study of mechanisms of chiral discrimination of amino acids and their derivatives on a teicoplanin-based chiral stationary phase

Cavazzini

Nadalini

Dondi

et al. 2004

Journal of Chromatography A

104

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Section: Amino Acidsmentioning

confidence: 99%

Section: Amino Acidsmentioning

confidence: 99%

Study of mechanisms of chiral discrimination of amino acids and their derivatives on a teicoplanin-based chiral stationary phase

Cavazzini

Nadalini

Dondi

et al. 2004

Journal of Chromatography A

104

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“…The stochastic theory is able to fully characterize the SEC process since the peak profile as a function of elution time can be obtained by either analytical or numerical inversion of the CF [1, 23 27]. Moreover, all the conventional chromatographic quantities can be derived [24]. The definitions of those quantities with which we are concerned are reported in the following.…”

Section: Monopore Generai Modelmentioning

confidence: 99%

Experimental validation of the stochastic theory of size-exclusion chromatography: Retention on single and coupled columns

et al. 2003

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The experimental validation of the recently developed stochastic model of size-exclusion chromatography (SEC), interpreted as a random process in which macromolecules undergo a continuous exchange process between the moving zone between the packing particles and the stagnant zone inside the particles, is attempted on the basis of an extended data set of experimental chromatograms of polystyrene standards, with molar masses ranging from 0.16 to 2200 kDa, on five different columns with widely different pore sizes. Several features of experimental chromatograms of standards eluting within or outside the permeation range, such as band broadening, peak tailing and peak splitting are qualitatively interpreted at the light of the stochastic theory of SEC. Furthermore, some aspects such as the influence of sample polydispersity on peak broadeningand of the exclusion effect in the movingzone (hydrodynamic chromatographic effect) on retention are discussed.\ud A new chemometric procedure was developed for estimatingthe KSEC equilibrium distribution constant without a priori assumptions regarding the extraparticle column volume, V0 , and the total pore volume Vp . This procedure allowed to obtain an unified description of the large retention data set over different columns. All retention data belonging to calibration ranges of the various columns, followed quite similar calibration plots, under the form of KSEC = (1 – r)m, where r is the ratio of macromolecule size to pore size, with m values close to 3 for all columns. A similar approach was able to represent the behaviour of two connected column in series, with consistent values of the pertinent parameters, which validates the stochastic theory of SEC with two pore types of different sizes. Finally, this two-pore model and a mixed SEC-hydrodynamic chromatography model were compared to interpret retention data on single columns around the exclusion limits. The practical application of these approaches in routine analysis, e.g. for monitoring the column degradation during its use, is mentioned

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“…In chromatography, the diffusion described above is combined with a constant-velocity mobile-phase convection. Furthermore, since the distribution given by this model deviates from zero just in the vicinity of the hold-up time, the residence time of a molecule in the mobile phase is, therefore, modeled here with the following equation , where u is the linear velocity of the mobile phase. The discussion of this assumption will be given later.…”

Section: Theorymentioning

confidence: 99%

“…When the molecule travels along the column, the number of adsorption−desorption steps is governed by Poisson statistics. The CF for various mobile-phase velocity assumptions is discussed by Dondi et al For the CF of the residence time in the column, they obtained the following generic expression: where Φ m is the CF of the time spent in the mobile phase and Φ r is the CF of the residence time in the column on a time scale normalized with respect to t 0 .…”

Section: Theorymentioning

confidence: 99%

Stochastic−Dispersive Theory of Chromatography

et al. 1999

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The stochastic model of chromatography has been combined with mobile-phase dispersion. With the combined model, both the effect of slow mass transfer or adsorption-desorption kinetics and dispersion on the band profile can be characterized. The stochastic model of chromatography is addressed with the characteristic function method. The moments of the peaks are calculated analytically for homogeneous and heterogeneous surfaces. It is shown that even in cases when the characteristic function cannot be calculated in closed form, the moments of the peak, and therefore the retention time, the number of theoretical plates, the peak asymmetry, can be calculated with simple expressions. Therefore, a full description of the chromatographic peak is available for homogeneous and any heterogeneous surfaces provided that the distribution of the sorption energies is known.

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Stochastic Theory of Chromatography: The Characteristic Function Method and the Approximation of Chromatographic Peak Shape

Cited by 18 publications

References 15 publications

Study of mechanisms of chiral discrimination of amino acids and their derivatives on a teicoplanin-based chiral stationary phase

Study of mechanisms of chiral discrimination of amino acids and their derivatives on a teicoplanin-based chiral stationary phase

Experimental validation of the stochastic theory of size-exclusion chromatography: Retention on single and coupled columns

Stochastic−Dispersive Theory of Chromatography

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