TY  - JOUR
AU  - Tumpa, Anja
AU  - Misković, Stefan
AU  - Stanimirović, Zorica
AU  - Jančić-Stojanović, Biljana
AU  - Medenica, Mirjana
PY  - 2017
UR  - https://farfar.pharmacy.bg.ac.rs/handle/123456789/2792
AB  - When it is taken into account that hydrophilic interaction liquid chromatography (HILIC) as an analytical method is relatively young compared with the other techniques, retention modeling could still bring scientifically valuable data to the field. Therefore, in this paper, olanzapine and its 8 impurities were selected as a test mixture, considering that they have never been analyzed in HILIC before. Their investigation on 4 different HILIC columns (bare silica, cyanopropyl, diol and zwitterionic) has been performed. The mixture of 9 structurally similar substances allows the examination of complex HILIC retention behavior depending on the chemical properties of the analytes, as well as of the stationary phase. To describe the nature of the relationship between the retention and the stronger eluent content in the mobile phase, we fitted experimentally obtained data to several theoretical (localized adsorption, nonlocalized partition, quadratic, and mixed) models. Results show that the best fit is the quadratic model with the highest R-2 and cross-validated coefficient of determination (Q(2)) values, but its usage has some drawbacks. With the aim to improve the possibility to predict retention behavior in HILIC, a new empirical model was proposed. For that purpose, a spline interpolation technique was performed, by dividing the experimental range into several subdivisions. This type of interpolation was performed for the first time in the chromatographic field. The estimation of the polynomial equations was performed using Q(2) values. Obtained Q(2) values pointed out the goodness of fit of the model, as well as its good predictive capabilities. In the end, the prediction capabilities were experimentally verified, under randomly chosen conditions from the experimental range. The errors in prediction were all under 10%, which is satisfying for HILIC. In this paper, retention behavior of olanzapine and its 8 impurities was investigated on four HILIC columns (bare silica, cyanopropyl, diol, and zwitterionic). Experimentally obtained data were fitted to several theoretical (localized adsorption, nonlocalized partition, quadratic, and mixed) models. Furthermore, a new empirical model (spline interpolation) was proposed. This type of interpolation was performed for the first time in the chromatography. Obtained Q(2) values pointed out the goodness of fit of the model, as well as its good predictive capabilities.
PB  - Wiley, Hoboken
T2  - Journal of Chemometrics
T1  - Modeling of HILIC retention behavior with theoretical models and new spline interpolation technique
VL  - 31
IS  - 9
DO  - 10.1002/cem.2910
ER  - 

@article{
author = "Tumpa, Anja and Misković, Stefan and Stanimirović, Zorica and Jančić-Stojanović, Biljana and Medenica, Mirjana",
year = "2017",
abstract = "When it is taken into account that hydrophilic interaction liquid chromatography (HILIC) as an analytical method is relatively young compared with the other techniques, retention modeling could still bring scientifically valuable data to the field. Therefore, in this paper, olanzapine and its 8 impurities were selected as a test mixture, considering that they have never been analyzed in HILIC before. Their investigation on 4 different HILIC columns (bare silica, cyanopropyl, diol and zwitterionic) has been performed. The mixture of 9 structurally similar substances allows the examination of complex HILIC retention behavior depending on the chemical properties of the analytes, as well as of the stationary phase. To describe the nature of the relationship between the retention and the stronger eluent content in the mobile phase, we fitted experimentally obtained data to several theoretical (localized adsorption, nonlocalized partition, quadratic, and mixed) models. Results show that the best fit is the quadratic model with the highest R-2 and cross-validated coefficient of determination (Q(2)) values, but its usage has some drawbacks. With the aim to improve the possibility to predict retention behavior in HILIC, a new empirical model was proposed. For that purpose, a spline interpolation technique was performed, by dividing the experimental range into several subdivisions. This type of interpolation was performed for the first time in the chromatographic field. The estimation of the polynomial equations was performed using Q(2) values. Obtained Q(2) values pointed out the goodness of fit of the model, as well as its good predictive capabilities. In the end, the prediction capabilities were experimentally verified, under randomly chosen conditions from the experimental range. The errors in prediction were all under 10%, which is satisfying for HILIC. In this paper, retention behavior of olanzapine and its 8 impurities was investigated on four HILIC columns (bare silica, cyanopropyl, diol, and zwitterionic). Experimentally obtained data were fitted to several theoretical (localized adsorption, nonlocalized partition, quadratic, and mixed) models. Furthermore, a new empirical model (spline interpolation) was proposed. This type of interpolation was performed for the first time in the chromatography. Obtained Q(2) values pointed out the goodness of fit of the model, as well as its good predictive capabilities.",
publisher = "Wiley, Hoboken",
journal = "Journal of Chemometrics",
title = "Modeling of HILIC retention behavior with theoretical models and new spline interpolation technique",
volume = "31",
number = "9",
doi = "10.1002/cem.2910"
}

Tumpa, A., Misković, S., Stanimirović, Z., Jančić-Stojanović, B.,& Medenica, M.. (2017). Modeling of HILIC retention behavior with theoretical models and new spline interpolation technique. in Journal of Chemometrics
Wiley, Hoboken., 31(9).
https://doi.org/10.1002/cem.2910

Tumpa A, Misković S, Stanimirović Z, Jančić-Stojanović B, Medenica M. Modeling of HILIC retention behavior with theoretical models and new spline interpolation technique. in Journal of Chemometrics. 2017;31(9).
doi:10.1002/cem.2910 .

Tumpa, Anja, Misković, Stefan, Stanimirović, Zorica, Jančić-Stojanović, Biljana, Medenica, Mirjana, "Modeling of HILIC retention behavior with theoretical models and new spline interpolation technique" in Journal of Chemometrics, 31, no. 9 (2017),
https://doi.org/10.1002/cem.2910 . .