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D'Archivio A.A.,University of LAquila | Maggi M.A.,Via Novus | Ruggieri F.,University of LAquila
Journal of Chromatography A | Year: 2014

We combine computational molecular descriptors and variables related with the gas-chromatographic stationary phase into a comprehensive model able to predict the retention of solutes in external columns. To explore the quality of various approaches based on alternative column descriptors, we analyse the Kováts retention indices (RIs) of 90 saturated esters collected with seven columns of different polarity (SE-30, OV-7, DC-710, OV-25, XE-60, OV-225 and Silar-5CP). Cross-column retention prediction is evaluated on an internal validation set consisting of data of 40 selected esters collected with each of the seven columns, sequentially excluded from calibration. The molecular descriptors are identified by a genetic algorithm variable selection method applied to a large set of non-empirical structural quantities aimed at finding the best multi-linear quantitative structure-retention relationship (QSRR) for the column OV-25 having intermediate polarity. To describe the columns, we consider the sum of the first five McReynolds phase constants and, alternatively, the coefficients of the corresponding QSRRs. Moreover, the mean RI value for the subset of esters used in QSRR calibration or RIs of a few selected compounds are used as column descriptors. For each combination of solute and column descriptors, the retention model is generated both by multi-linear regression and artificial neural network regression. © 2014 Elsevier B.V. Source


D'Archivio A.A.,University of LAquila | Maggi M.A.,Via Novus | Ruggieri F.,University of LAquila
Journal of Pharmaceutical and Biomedical Analysis | Year: 2014

In the present work, the retention time (RT) of acylcarnitines, collected by ultra-performance liquid-chromatography after formation of butyl esters, is modelled by quantitative structure-retention relationship (QSRR) method. The investigated set consists of free carnitine and 46 different acylcarnitines, including the isomers commonly monitored in screening metabolic disorders. To describe the structure of (butylated) acylcarnitines, a large number of computational molecular descriptors generated by software Dragon are subjected to variable selection methods aimed at identifying a small informative subset. The QSRR model is established using two different approaches: the multi linear regression (MLR) combined with a genetic algorithm (GA) variable selection and the partial least square (PLS) regression after iterative stepwise elimination (ISE) of useless descriptors. Predictive performance of both models is evaluated using an external set consisting of 10 representative acylcarnitines, and, successively, by repeated random data partitions between the calibration and prediction sets. Finally, a principal component analysis (PCA) is performed on the model variables to facilitate the interpretation of the established QSRRs. A PLS model based on seven latent variables extracted from 20 molecular descriptors selected by ISE permits to calculate/predict the retention time of acylcarnitine with accuracy better than 5%, whereas a 6-dimensional model identified by GA-MLR provides a slightly worse performance. © 2014. Source


D'Archivio A.A.,University of LAquila | Maggi M.A.,Via Novus | Marinelli C.,University of LAquila | Ruggieri F.,University of LAquila | Stecca F.,Dell
Journal of Chromatography A | Year: 2015

A response surface methodology (RSM) approach is applied to optimise the temperature-programme gas-chromatographic separation of 16 organochloride pesticides, including 12 compounds identified as highly toxic chemicals by the Stockholm Convention on Persistent Organic Pollutants. A three-parameter relationship describing both linear and curve temperature programmes is derived adapting a model previously used in literature to describe concentration gradients in liquid chromatography with binary eluents. To investigate the influence of the three temperature profile descriptors (the starting temperature, the gradient duration and a shape parameter), a three-level full-factorial design of experiments is used to identify suitable combinations of the above variables spanning over a useful domain. Resolutions of adjacent peaks are the responses modelled by RSM using two alternative methods: a multi-layer artificial network (ANN) and usual polynomial regression. The proposed ANN-based approach permits to model simultaneously the resolutions of all the consecutive analyte pairs as a function of the temperature profile descriptors. Four critical pairs giving partially overlapped peaks are identified and multiresponse optimisation is carried out by analysing the surface plot of a global resolution defined as the average of the resolutions of the critical pairs. Descriptive/predictive performance and applicability of the ANN and polynomial RSM methods are compared and discussed. © 2015 Elsevier B.V. Source


D'Archivio A.A.,University of LAquila | Maggi M.A.,Via Novus | Ruggieri F.,University of LAquila | Carlucci M.,University of Chieti Pescara | And 2 more authors.
Journal of Pharmaceutical and Biomedical Analysis | Year: 2016

A procedure based on microextraction by packed sorbent (MEPS) followed by ultra-high performance liquid chromatography (UHPLC) with photodiode array (PDA) detection has been developed for the analysis of seven selected non steroidal anti-inflammatory drugs (NSAIDs) in human dialysates. The influence on MEPS efficiency of pH of the sample, pH of the washing solvent and methanol content in the hydro-alcoholic elution mixture has been investigated by response surface methodology based on a Box-Behnken design of experiments. Among the above factors, pH of sample is the variable that mostly influences MEPS recovery. UHPLC separation of the NSAIDs was completed within less than 4 min under isocratic elution conditions on a Fortis SpeedCore C18 column (150 × 4.6 mm I.D., 2.6 μm) using acetonitrile-phosphate buffer as the mobile phase. Calibration curves of the NSAIDs were linear over the concentration range 0.025-15 μg/mL, with correlation coefficients ≥ 0.998. Intra- and inter-assay relative standard deviations were <8% and recovery values ranged from 94% to 100% for the quality control samples. The results reveal that the developed MEPS/PDA-UHPLC method exhibits a good accuracy and precision and is well suited for the rapid analysis of human dialysate from patients treated with the selected NSAIDs. © 2016 Elsevier B.V. Source


Ruggieri F.,Aquila | D'Archivio A.A.,Aquila | Di Camillo D.,Aquila | Lozzi L.,Aquila | And 3 more authors.
Journal of Separation Science | Year: 2015

Novel polystyrene-based molecularly imprinted polymer nanofibers were synthesized through the electrospinning technique. The molecularly imprinted polymers were prepared using a non-covalent approach and atrazine as template. For comparison, nonimprinted polymer nanofibers were also synthesized. The morphology of the synthesized nanofibers was characterized using scanning electron microscopy. The adsorption of pesticides, atrazine, atrazine desisopropyl, atraton, carboxin, linuron, and chlorpyrifos was studied under equilibrium (batch) conditions. To describe the adsorption capability of the synthesized polymers, Langmuir and Freundlich models were used. The Freundlich model provided a better mathematical approximation of the sorption characteristic for polymers nanofibers. To evaluate the adsorption capacity in the presence of interferents experiments on river water samples spiked with a mixture of six pesticides were also performed. The results obtained for the highest concentration levels investigated, show a greater amount of pesticide adsorbed on molecularly imprinted polymers and non-imprinted polymers compared to those obtained using commercial stationary phases used as reference. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Source

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