title: Development of an inorganic cations retention model in ion chromatography by means of artificial neural networks with different two-phase training algorithms.
abstract: This paper describes development of artificial neural network (ANN) retention model, which can be used for method development in variety of ion chromatographic applications. By using developed retention model it is possible both to improve performance characteristic of developed method and to speed up new method development by reducing unnecessary experimentation. Multilayered feed forward neural network has been used to model retention behaviour of void peak, lithium, sodium, ammonium, potassium, magnesium, calcium, strontium and barium in relation with the eluent flow rate and concentration of methasulphonic acid (MSA) in eluent. The probability of finding the global minimum and fast convergence at the same time were enhanced by applying a two-phase training procedure. The developed two-phase training procedure consists of both first and second order training. Several training algorithms were applied and compared, namely: back propagation (BP), delta-bar-delta, quick propagation, conjugate gradient, quasi Newton and Levenberg-Marquardt. It is shown that the optimized two-phase training procedure enables fast convergence and avoids problems arisen from the fact that every new weight initialization can be regarded as a new starting position and yield irreproducible neural network if only second order training is applied. Activation function, number of hidden layer neurons and number of experimental data points used for training set were optimized in order to insure good predictive ability with respect to speeding up retention modelling procedure by reducing unnecessary experimental work. The predictive ability of optimized neural networks retention model was tested by using several statistical tests. This study shows that developed artificial neural network are very accurate and fast retention modelling tool applied to model varied inherent non-linear relationship of retention behaviour with respect to mobile phase parameters.
authors.affiliation: University of Zagreb, Faculty of Chemical Engineering and Technology, Laboratory of Analytical Chemistry, Marulićev trg 20, 10000 Zagreb, Croatia. tomislav.bolanca@fkit.hr
authors.forename: Tomislav
authors.initials: T
authors.lastname: Bolanca
authors.forename: Stefica
authors.initials: S
authors.lastname: Cerjan-Stefanović
authors.forename: Melita
authors.initials: M
authors.lastname: Regelja
authors.forename: Hrvoje
authors.initials: H
authors.lastname: Regelja
authors.forename: Sven
authors.initials: S
authors.lastname: Loncarić
mesh_terms: D000465:Algorithms; D001464:Barium / Q000737:chemistry; D002118:Calcium / Q000737:chemistry; D002412:Cations / Q000737:chemistry*; D002853:Chromatography, Liquid / Q000379:methods*; D007477:Ions / Q000737:chemistry; D008094:Lithium / Q000737:chemistry; D008274:Magnesium / Q000737:chemistry; D016571:Neural Networks, Computer; D011188:Potassium / Q000737:chemistry; D000644:Quaternary Ammonium Compounds / Q000737:chemistry; D015203:Reproducibility of Results; D012964:Sodium / Q000737:chemistry; D013324:Strontium / Q000737:chemistry; D013997:Time Factors
chemical_list: D002412:Cations; D007477:Ions; D000644:Quaternary Ammonium Compounds; D001464:Barium; D008094:Lithium; D012964:Sodium; D008274:Magnesium; D011188:Potassium; D002118:Calcium; D013324:Strontium