showing 46 related works from this author
Systematic Approach To Calculate the Concentration of Chemical Species in Multi-Equilibrium Problems
2010
A general systematic approach is proposed for the numerical calculation of multi-equilibrium problems. The approach involves several steps: (i) the establishment of balances involving the chemical species in solution (e.g., mass balances, charge balance, and stoichiometric balance for the reaction products), (ii) the selection of the unknowns (the concentration of selected chemical species at equilibrium), (iii) the estimation of the concentration of the other species based on the selected species and the equilibrium expressions, and (iv) the minimization of the sum of the squared balances (search of the optimal combination of the unknowns). The application of the systematic approach to cas…
New approaches based on modified Gaussian models for the prediction of chromatographic peaks
2012
Abstract The description of skewed chromatographic peaks has been discussed extensively and many functions have been proposed. Among these, the Polynomially Modified Gaussian (PMG) models interpret the deviations from ideality as a change in the standard deviation with time. This approach has shown a high accuracy in the fitting to tailing and fronting peaks. However, it has the drawback of the uncontrolled growth of the predicted signal outside the elution region, which departs from the experimental baseline. To solve this problem, the Parabolic-Lorentzian Modified Gaussian (PLMG) model was developed. This combines a parabola that describes the variance change in the peak region, and a Lor…
Influence of the addition of modifiers on solute-micelle interaction in hybrid micellar liquid chromatography
1998
In reversed-phase micellar liquid chromatography (MLC) organic modifiers are usually added to the mobile phase to modify the eluent strength and to increase the efficiency of the chromatographic peaks. The effect of the modifiers methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, acetonitrile and tetrahydrofuran on the critical micelle concentration (cmc) of the anionic surfactant sodium dodecylsulphate (SDS) has been studied to enable understanding of the interactions between solute, micelles and bulk liquid in such hybrid eluents. Methanol, acetonitrile and tetrahydrofuran increased thecmc, whereas the other alcohols reduced its value. For butanol and pentanol, which partition into the…
Data Treatment and Error Analysis in Kinetics
2000
Methods of data treatment in kinetics are reviewed from a practical viewpoint. The equations to describe the kinetics of chemical reactions and the methodology to obtain the models are presented. Moreover, the integration methods that are needed for the simulation of complex reactions are explained, from the simple first-order reaction to the complex general mechanism. However, it is essential to know the main sources of error in data treatment in order to reduce their effects on the results. Stress is put on the analysis of the errors due to the simplification of complex models. The different factors that influence the kinetics of the reaction are reviewed. How to take advantage of the kin…
EVALUATION OF THE ELUTION STRENGTH OF THE SURFACTANT AND ORGANIC SOLVENT IN HYBRID MICELLAR MOBILE PHASES
2001
The global ability of a mixed mobile phase (with two or more modifiers) to elute a solute is often measured without distinguishing between the elution strength of each modifier. An algorithm is proposed to evaluate the elution strength of the modifiers in hybrid micellar mobile phases containing a surfactant and an organic solvent. The algorithm is based on a mechanistic retention model that takes into account the competing equilibria of solutes among aqueous-organic phase, micelle, and stationary phase. The change in the elution strength of surfactant and organic solvent with respect to the concentration of both modifiers is also examined. The results are discussed according to the values …
Description of the retention behaviour in micellar liquid chromatography as a function of pH, surfactant and modifier concentration
1997
Abstract Micellar liquid chromatography permits the elution of solutes of diverse polarity. One of the most outstanding advantages of the technique is its capability of predicting the retention with high accuracy, as a function of different experimental variables. The separation of a group of compounds is usually optimized by varying the concentrations of surfactant and modifier in the mobile phase. The pH is, however, for many solutes, a variable that should be considered in the description of their elution behaviour. A global model that takes into account, simultaneously, the concentrations of surfactant and modifier, and the pH as chromatographic variables, is proposed for ionizable solu…
Approaches to model the retention and peak profile in linear gradient reversed-phase liquid chromatography.
2012
Abstract The optimisation of the experimental conditions in gradient reversed-phase liquid chromatography requires reliable algorithms for the description of the retention and peak profile. As in isocratic elution, the linear relationship between the logarithm of the retention factor and the solvent contents is only acceptable in relatively small concentration ranges of modifier. However, more complex models may not allow an analytical integration of the general equation for gradient elution. Alternative approaches for modelling the retention in linear gradient elution are here proposed. Those based on the quadratic logarithmic model and a model proposed for normal liquid chromatography yie…
On the Measurement of Dead Time in Micellar Liquid Chromatography
1996
Abstract Modelling of the retention of solutes in micellar liquid chromatography allows the optimization of the resolution of a mixture of solutes and the determination of physico-chemical retention parameters. Both tasks imply the calculation of capacity factors, which are severely affected by the value of dead time. However, the determination of the dead time is not easy when a micellar mobile phase is used owing to the wide and variable perturbations that appear at the heads of the chromatograms. Four different criteria of determination of a reference time in the chromatograms are proposed and compared. The criteria are applied to mobile phases containing a varying concentration of surfa…
Approaches to estimate the time and height at the peak maximum in liquid chromatography based on a modified Gaussian model
2011
The time and height at the peak maximum are key parameters to describe a chromatographic peak with prediction or optimization purposes, or in the qualitative/quantitative analysis of samples. Three different approaches to estimate these parameters, using the experimental points in the peak maximum region, are here described and compared. The approaches are based on the reliable description of the peak profile using a modified Gaussian model with a parabolic variance (PVMG). In the first approach, non-linear fitting of the chromatographic data to the PVMG model is carried out to obtain the time and height at the peak maximum (Approach I). In the other two approaches, the PVMG model is linear…
Modelling of retention behaviour of solutes in micellar liquid chromatography
1997
In micellar liquid chromatography (MLC), the resolution for a given multi-component mixture can be optimized by changing several variables, such as the concentrations of surfactant and organic modifier, the pH and temperature. However, this advantage can only be fully exploited with the development of mathematical models that describe the retention and the separation mechanisms. Several reports have appeared recently on the possibilities of accurately predicting the solute retention in MLC. Although the retention and selectivity may strongly change with varying concentrations of surfactant, organic modifier and/or pH, the observed changes are very regular, and are well described by simple m…
Combined effect of solvent content, temperature and pH on the chromatographic behaviour of ionisable compounds. III: Considerations about robustness
2009
Abstract We previously reported a model able to predict the retention time of ionisable compounds as a function of the solvent content, temperature and pH [J. Chromatogr. A 1163 (2007) 49]. The model was applied further, developing an optimisation of the resolution based on the peak purity concept [J. Chromatogr. A 1193 (2008) 117]. However, we left aside an important issue: we did not consider incidental overlaps caused by shifts in the predicted peak positions, owing either to uncertainties in the source data, modelling errors, or the practical implementation in the chromatograph of the optimal mobile phase (or any other). These shifts can ruin the predicted separation, since they can eas…
Isocratic and gradient elution in micellar liquid chromatography with Brij-35
2015
Polyoxyethylene(23)lauryl ether (known as Brij-35) is a nonionic surfactant, which has been considered as an alternative to the extensively used in micellar liquid chromatography anionic surfactant sodium lauryl (dodecyl) sulfate, for the analysis of drugs and other types of compounds. Brij-35 is the most suitable nonionic surfactant for micellar liquid chromatography, owing to its commercial availability, low cost, low toxicity, high cloud temperature, and low background absorbance. However, it has had minor use. In this work, we gather and discuss some results obtained in our laboratory with several β-blockers, sulfonamides, and flavonoids, concerning the use of Brij-35 as mobile phase mo…
Protocol to compare column performance applied to hydrophilic interaction liquid chromatography
2019
Abstract The lack of retention of highly polar solutes in liquid chromatography with reversed phase columns (RPLC) can be solved through the use of the hydrophilic interaction liquid chromatographic (HILIC) mode. Due to the complexity of the separation mechanisms in HILIC and the different factors that may have significant influence, the selection of the appropriate stationary phase plays a fundamental role in the development of analytical procedures to obtain good performance. In this work, the chromatographic performance of bare silica and six polar stationary phases with different functionalized groups (with neutral, cationic, anionic and zwitterionic character) are investigated. The beh…
Study of elution behaviour with gradient voltage in CEC using methacrylate monolithic columns.
2010
A theoretical study on the retention behaviour and chromatographic performance of neutral solutes using a lauryl methacrylate-based monolithic column under voltage gradient mode in CEC was carried out. Through a flexible mathematical function based on a modified Gaussian model, the peak shape of compounds was firstly fitted under constant and gradient voltage. Using the peak shape parameters and retention time, the estimation of global chromatographic performance, efficiency and peak capacity under several voltage conditions was performed. The influence of voltage gradient on the separation efficiency is discussed and simple equations are presented to calculate retention and peak widths und…
Micellar liquid chromatographic separation of amino acids using pre- and post-column o -phthalaldehyde/ N -acetylcysteine derivatization
2000
Abstract The isocratic analysis of primary proteic amino acids using a C18 column, micellar mobile phases of sodium dodecyl sulphate (SDS) and 1-propanol at varying pH, and pre- and post-column formation of the o-phthalaldehyde (OPA)/N-acetyl- l -cysteine (NAC) isoindoles, is examined. An interpretive optimization strategy was applied to find the best separation conditions. For this purpose, empirical polynomial models were used to describe the elution behavior of the isoindoles and free amino acids, using as separation factors the concentrations of surfactant and modifier (two-factor problem), or these two factors and the pH of the mobile phase (three-factor problem). The separation of the…
Global treatment of chromatographic data with MICHROM
1997
Abstract The program MICHROM for the general treatment of chromatographic data is presented. MICHROM takes part in all the stages of the analytical process. It allows determination of dead time, smoothing of chromatograms, measurement of peak parameters, fitting of skewed peaks, and deconvolution of overlapped peaks. Tools for the experimental design, optimization of the mobile phase composition to resolve a mixture of analytes, and simulation of chromatograms in several experimental conditions, are implemented. Routines for the graphical representation of chromatograms, resolution surfaces, contour maps, management of data series, optimization and regression analysis, are also included. Th…
Analysis of the sensitivity to the systematic error in least-squares regression models
2004
An algorithm that calculates the sensitivity to the systematic error of the fitted parameters of a least-squares regression model, with respect to the known parameters, is developed. The algorithm can be applied to mechanistic and empirical models, obtained by linear and non-linear regression, including principal component and partial least-squares. It can be useful in identifying those parameters or calibration regions that can influence other parameters and the response mostly, and thus, whose accuracy should be particularly procured. Other applications are the weighing of experimental points and the comparison of different models and regression methods in terms of its ability of amplifyi…
Prediction of peak shape as a function of retention in reversed-phase liquid chromatography
2004
Optimisation of the resolution of multicomponent samples in HPLC is usually carried out by changing the elution conditions and considering the variation in retention of the analytes, to which a standard peak shape is assigned. However, the change in peak shape with the composition of the mobile phase can ruin the optimisation process, yielding unexpected overlaps in the experimental chromatograms for the predicted optimum, especially for complex mixtures. The possibility of modelling peak shape, in addition to peak position, is therefore attractive. A simple modified-Gaussian model with a parabolic variance, which is a function of conventional experimental parameters: retention time (tR), p…
A three-factor optimisation strategy for micellar liquid chromatography
2000
An interpretive optimisation methodology for micellar liquid chromatography (MLC) is shown, taking into account pH, surfactant (sodium dodecyl sulphate) and organic modifier (propanol) concentration. Two objectives are considered: to develop a highly practical straightforward three-factor optimisation for practical MLC, and, in order to avoid unecessary experiments, to link two and three-factor optimisations through a step-wise construction of the experimental design at different pH levels. The whole pH range for an ODS column (from 3 to 7) is covered. The proposed strategy was thoroughly evaluated using the chromatographic data from 81 experimental mobile phases, applied to the separation …
Description of the Retention and Peak Profile for Chromolith Columns in Isocratic and Gradient Elution Using Mobile Phase Composition and Flow Rate a…
2014
The effect of the modifier concentration and flow rate on the chromatographic performance of a second generation Chromolith® RP-18e column, under isocratic and gradient elution with acetonitrile-water mixtures, was examined using four sulphonamides as probe compounds. The acetonitrile concentration was varied between 5 and 55% (v/v), and the flow rate between 0.1 and 5.0 mL/min, keeping the other factors constant. The changes in both retention and peak profile were modelled, and used to build simple plots, where the logarithm of the retention factor was represented against the modifier concentration (in gradient elution, against the initial modifier concentration), and the half-widths or wi…
Some insights on the description of gradient elution in reversed-phase liquid chromatography
2014
The so-called "fundamental equation for gradient elution" has been used for modeling the retention in gradient elution. In this approach, the instantaneous retention factor (k) is expressed as a function of the change in the modifier content (φ(ts )), ts being the time the solute has spent in the stationary phase. This approach can only be applied at constant flow rate and with gradients where the elution strength depends on the column length following a f(t-l/u) function, u being the linear mobile phase flow rate, and l the distance from the column inlet to the location where the solute is at time t measured from the beginning of the gradient. These limitations can be solved by using the h…
A theoretical plate model accounting for slow kinetics in chromatographic elution.
2011
The chromatographic elution has been studied from different perspectives. However, in spite of the simplicity and evident deficiencies of the plate model proposed by Martin and Synge, it has served as a basis for the characterization of columns up-to-date. This approach envisions the chromatographic column as an arbitrary number of theoretical plates, each of them consisting of identical repeating portions of mobile phase and stationary phase. Solutes partition between both phases, reaching the equilibrium. Mobile phase transference between the theoretical plates is assumed to be infinitesimally stepwise (or continuous), giving rise to the mixing of the solutions in adjacent plates. This yi…
Peak capacity estimation in isocratic elution.
2008
Peak capacity (i.e. maximal number of resolved peaks that fit in a chromatographic window) is a theoretical concept with growing interest, but based on a situation rarely met in practice. Real chromatograms tend to have uneven distributions, with overlapped peaks and large gaps. The number of resolved compounds should, therefore, be known from estimations. Several equations have been reported for this purpose based on three perspectives, namely, the intuitive approach (peak capacity as the size of the retention time window measured in peak width units), which assumes peaks with the same width, and the outlines of Giddings and Grushka, which consider changes in peak width with retention time…
MICELLAR CHROMATOGRAPHIC PROCEDURE WITH DIRECT INJECTION FOR THE DETERMINATION OF SULFONAMIDES IN MILK AND HONEY SAMPLES
2001
The capability of liquid chromatography with micellar mobile phases of sodium dodecyl sulfate (SDS), of allowing the direct injection of biological fluids into reversed-phase columns, was applied to the determination of sulfonamides in milk and honey samples. The chromatographic behavior of a group of 15 sulfonamides was studied at pH 3.0 where the drugs showed a greater separation space. Acetonitrile was added to the mobile phase to decrease the retention of the most hydrophobic drugs and increase the efficiencies, which yielded a higher resolution. The samples were diluted with 0.10 M SDS to facilitate the solubilization of the matrix compounds and release the protein-bound drugs. The pro…
Models and objective functions for the optimisation of selectivity in reversed-phase liquid chromatography.
2006
Interpretive methodologies are the most efficient tools for finding the optimal conditions in chromatography. These methodologies are supported by models or algorithms able to infer the system behaviour upon changes in the experimental factors. Once the models are built with data obtained from sets of carefully designed experiments, molecular modelling or other approaches, they can be applied to predict the performance of new conditions. The different elements involved in these methodologies, for both isocratic and gradient elution, are given. Special attention is devoted to the description of retention, owing to its major impact on the prediction of chromatographic resolution. Several mode…
Parabolic-Lorentzian modified Gaussian model for describing and deconvolving chromatographic peaks.
2002
Abstract A new mathematical model for characterising skewed chromatographic peaks, which improves the previously reported polynomially modified Gaussian (PMG) model, is proposed. The model is a Gaussian based equation whose variance is a combined parabolic-Lorentzian function. The parabola accounts for the non-Gaussian shaped peak, whereas the Lorentzian function cancels the variance growth out of the elution region, which gives rise to a problematic baseline increase in the PMG model. The proposed parabolic-Lorentzian modified Gaussian (PLMG) model makes a correct description of peaks showing a wide range of asymmetry with positive and/or negative skewness. The new model is shown to give b…
Data Treatment in Kinetics
2000
Chemical kinetics is an important part of chemistry devoted to study how reactions proceed and quantify the rate of the process. The reaction mechanism is the chemical model that describes how the chemical change occurs. From the proposed mechanism, a mathematical model can be obtained to explain the evolution of the chemical species with time. In many cases, the mechanism can be simplified to a single rate law that relates the reaction rate with concentrations. In the last decades, the study of kinetic systems has benefited from the development of instrumentation, the increasing availability of specialized computer software, and the advances in data treatment techniques. A comprehensive re…
Combined effect of solvent content, temperature and pH on the chromatographic behaviour of ionisable compounds.
2008
The organic solvent content and the pH in the mobile phase are the usual main factors in reversed-phase liquid chromatographic separations, owing to their strong effects on retention and/or selectivity. Temperature is often neglected. However, even in cases where the impact of this factor on selectivity is minor, the reduction in analysis time is still an interesting reason to consider it. In addition, ionisable compounds may exhibit selectivity changes, owing to the interaction of organic solvent and/or temperature with pH. The separation of ionisable compounds (nine diuretics: bendroflumethiazide, benzthiazide, bumetanide, chlorthalidone, furosemide, piretanide, probenecid, trichloromethi…
A new mathematical function for describing electrophoretic peaks.
2005
A new model is proposed for characterizing skewed electrophoretic peaks, which is a combination of leading and trailing edge functions, empirically modified to get a rapid recovery of the baseline. The peak model is a sum of square roots and is called thereby "combined square roots (CSR) model". The flexibility of the model was checked on theoretical and experimental peaks with asymmetries in the range of 0-10 (expressed as the ratio of the distance between the center and the trailing edge, and the center and the leading edge of the chromatographic peak, measured at 10% of peak height). Excellent fits were found in all cases. The new model was compared with other three models that have show…
Prediction of Peak Shape and Characterization of Column Performance in Liquid Chromatography as a Function of Flow Rate
2015
Traditionally, column performance in liquid chromatography has been studied using information from the elution of probe compounds at different flow rates through van Deemter plots, which relate the column plate height to the linear mobile phase velocity. A more recent approach to characterize columns is the representation of the peak widths (or the right and left peak half-widths) for a set of compounds versus their retention times, which, for isocratic elution, give rise to almost linear plots. In previous work, these plots have been shown to facilitate the prediction of peak profiles (width and asymmetry) with optimization purposes. In this work, a detailed study on the dependence of the …
Half-width plots, a simple tool to predict peak shape, reveal column kinetics and characterise chromatographic columns in liquid chromatography: Stat…
2013
Peak profiles in chromatography are characterised by their height, position, width and asymmetry; the two latter depend on the values of the left and right peak half-widths. Simple correlations have been found between the peak half-widths and the retention times. The representation of such correlations has been called half-width plots. For isocratic elution, the plots are parabolic, although often, the parabolas can be approximated to straight-lines. The plots can be obtained with the half-widths/retention time data for a set of solutes experiencing the same kinetics, eluted with a mobile phase at fixed or varying composition. When the analysed solutes experience different resistance to mas…
Performance and modelling of retention in microemulsion liquid chromatography
2020
Abstract The capability of liquid chromatography with microemulsions (MEs) as mobile phases was studied for the analysis of four parabens (butylparaben, ethylparaben, methylparaben, and propylparaben) and seven β-adrenoceptor antagonists (acebutolol, atenolol, carteolol, metoprolol, oxprenolol, propranolol, and timolol). MEs were formed by mixing aqueous solutions of the anionic surfactant sodium dodecyl sulphate, the alcohol 1-butanol that played the role of co-surfactant, and octane as oil. In order to guarantee the formation of stable MEs, a preliminary study was carried out to determine the appropriate ranges of concentrations of the three components. For this purpose, mixtures of varia…
Study of the column efficiency using gradient elution based on Van Deemter plots.
2018
Performance of chromatographic columns is of major importance in the development of more efficient separation methods. So far, a common practice is to study the column behavior in isocratic elution by modifying the flow rate and fitting the theoretical plate height values versus the mobile phase linear velocity, according to the Van Deemter equation. In this work, an approach is presented to extend the measurement of efficiency to linear gradient elution, where the mean retention factor is kept constant at each assayed flow. This avoids a possible source of uncertainty due to the change in the distribution equilibria profile, and makes the mean interactions with the stationary phase in grad…
Pointwise resolutive significance of data and applications in experimental design and data treatment
1992
Abstract The concept of the resolutive significance of a point in a data set with regard to a number of addressed parameters is introduced, and two algorithms able to measure it are proposed. The algorithms are validated using simulated experiments. The sum of all the pointwise resolutive significances of a data set is also proposed as a measure of the resolution of the data set. This sum correlates well with the reciprocal of the standard deviation of the fitted parameters, indicating the precision that can be expected for each parameters. Applications in experimental design, and a method for establishing the weights in the least-quarters regression analysis are discussed.
Peak dispersion in gradient elution: An insight based on the plate model.
2020
Gradient elution in liquid chromatography reduces the analysis time, improves the efficiency and increases the peak capacity. The study of this chromatographic mode has been based mainly on kinetic dispersion models. The plate model has been applied to a lesser extent, despite being the basis for the concepts of plate height and chromatographic efficiency. In this work, a general equation describing peak dispersion in HPLC gradient elution is derived from the plate model. This equation is studied and validated for three types of gradients: (i) a reference gradient without ramp in which the retention factor varies with time identically throughout the column, (ii) a gradient of stationary pha…
Systematic Approach for Calculating the Concentrations of Chemical Species in Multiequilibrium Problems: Inclusion of the Ionic Strength Effects
2012
A general systematic approach including ionic strength effects is proposed for the numerical calculation of concentrations of chemical species in multiequilibrium problems. This approach extends the versatility of the approach presented in a previous article and is applied using the Solver option of the Excel spreadsheet to solve real problems such as the calculation of the pH of buffer solutions at any ionic strength. It is useful for undergraduate programs, in post-graduate programs, and in professional laboratories to predict experimental conditions.
Second-order tensorial calibration for kinetic spectrophotometric determination
1996
Abstract Kinetic-diode array spectrophotometric detection, as well as other multichannel techniques when used in non-equilibrium conditions, constitute second-order instrumentation. The second-order response provided will be bilinear, under certain conditions even trilinear, thus allowing the use of the generalized rank annihilation method (GRAM) and the trilinear decomposition method (TLD). Both numerically simulated and experimental data were used to evaluate the performance of these calibration techniques. The conditions in which the ‘second-order advantage’ (the possibility of quantifying the analytes in the presence of unknown reactions or interferences) is preserved were investigated.…
Approaches to characterise chromatographic column performance based on global parameters accounting for peak broadening and skewness.
2009
Peak broadening and skewness are fundamental parameters in chromatography, since they affect the resolution capability of a chromatographic column. A common practice to characterise chromatographic columns is to estimate the efficiency and asymmetry factor for the peaks of one or more solutes eluted at selected experimental conditions. This has the drawback that the extra-column contributions to the peak variance and skewness make the peak shape parameters depend on the retention time. We propose and discuss here the use of several approaches that allow the estimation of global parameters (non-dependent on the retention time) to describe the column performance. The global parameters arise f…
Reversed Phase Liquid Chromatography
2015
Prediction of peak shape in hydro-organic and micellar-organic liquid chromatography as a function of mobile phase composition
2007
A simple model is proposed that relates the parameters describing the peak width with the retention time, which can be easily predicted as a function of mobile phase composition. This allows the further prediction of peak shape with global errors below 5%, using a modified Gaussian model with a parabolic variance. The model is useful in the optimisation of chromatographic resolution to assess an eventual overlapping of close peaks. The dependence of peak shape with mobile phase composition was studied for mobile phases containing acetonitrile in the presence and absence of micellised surfactant (micellar-organic and hydro-organic reversed-phase liquid chromatography, RPLC). In micellar RPLC…
Characterization of chromatographic peaks using the linearly modified Gaussian model. Comparison with the bi-Gaussian and the Foley and Dorsey approa…
2017
To characterize column performance in liquid chromatography, several parameters must be obtained from experimental data. These parameters can be computed through the numerical integration of the net signal to calculate the moments after subtraction of the baseline. This requires the establishment of the peak integration limits. The whole process introduces significant uncertainty. For this reason, several alternative procedures have been proposed to measure the area, mean time and variance, based on the assumption that the chromatographic peak can be described with a mathematical function. This allows the calculation of the peak position and variance making use of the values of the experime…
Extension of the linear solvent strength retention model including a parameter that describes the elution strength changes in liquid chromatography.
2020
Modelling the retention behaviour of solutes in liquid chromatography, based on the composition of the mobile phase is a common task in the chromatographic practice. Along the development of liquid chromatography (LC), several models have been proposed to help in understanding the retention mechanisms, and especially, allow the prediction of retention times with optimisation purposes. Particular models are used for different LC modes, such as normal phase (NPLC), reversed phase (RPLC), hydrophilic interaction (HILIC), and micellar (MLC). In this work, a general equation is proposed that includes a parameter (the elution degree, g), which characterises the way the elution strength varies wit…
Modified Gaussian models applied to the description and deconvolution of peaks in chiral liquid chromatography.
2020
Abstract The description of the profiles of chromatographic peaks has been studied extensively, with a large number of proposed mathematical functions. Among them, the accuracy achieved with modified Gaussian models that describe the deviation of an ideal Gaussian peak as a change in the peak variance or standard deviation over time, has been highlighted. These models are, in fact, a family of functions of different complexity with great flexibility to adjust chromatographic peaks over a wide range of asymmetries and shapes. However, an uncontrolled behaviour of the signal may occur outside the region being fitted, forcing the use of different strategies to overcome this problem. In this wo…
Some observations on the prediction of retention in reversed-phase liquid chromatography using the pH as main factor
2004
Abstract When solutes show acid–base behaviour inside the working pH of a reversed-phase liquid chromatographic (RPLC) column, besides the type and percentage of organic modifier, pH can be included to improve the possibilities of separation. Optimisation based on a retention model is an economical and reliable way to achieve the best resolution. However, the difficulties found in knowing the exact pH values and the dependence of acid−base constants of solutes with mobile phase composition makes the accurate modelling of the retention behaviour as a function of these variables rather difficult. In this work, it is shown that in fact, there is no need to have this information. Based on the e…
Modelling and prediction of retention in high-performance liquid chromatography by using neural networks
1995
Multi-layer feed-forward neural networks trained with an error back-propagation algorithm have been used to model retention behaviour of liquid chromatography as a function of the composition of the mobile phases. Conventional hydro-organic and micellar mobile phases were considered. Accurate retention modelling and prediction have been achieved using mobile phases defined by two, three and four parameters. With micellar mobile phases, the parameters involved included the concentrations of surfactant and organic modifier, pH and temperature. It is shown that neural networks provide a competitive tool to model varied inherent nonlinear relationships of retention behaviour with respect to the…
Study of peak shape and efficiency in butyl acrylate-based monolithic columns for capillary electrochromatography.
2009
Abstract The study and modelling peak shape of in capillary electrochromatography (CEC), obtained using butyl acrylate (BA)-based monolithic columns, is described in this article. A modified-Gaussian model, which is a function of conventional experimental parameters: retention time (tR), peak height (H0) and standard deviation (σ0) at the peak maximum, and left (A) and right (B) halfwidths, was used to describe the peaks of thiourea and several polyaromatic hydrocarbons compounds, which were eluted under several applied voltages. A mean relative error below 2% in the prediction of peak shape is obtained. Based on peak parameters, an easy and reliable estimation of global chromatographic per…