Aplicación de un gestor de tareas colaborativo (Trello) para la tutorización de Trabajos de Fin de Grado y Trabajos de Fin de Máster en la Facultad de Ciencias

Póster presentado en: VIII Jornadas de Innovación Docente de la UBU, Burgos, 5 de abril de 2016, organizadas por el Instituto de Formación e Innovación Educativa-IFIE de la Universidad de Burgo

Immobilization of Acetylcholinesterase on Screen-Printed Electrodes. Application to the Determination of Arsenic(III)

Enzymatic amperometric procedures for measuring arsenic, based on the inhibitive action of this metal on acetylcholinesterase enzyme activity, have been developed. Screen-printed carbon electrodes (SPCEs) were used with acetylcholinesterase covalently bonded directly to its surface. The amperometric response of acetylcholinesterase was affected by the presence of arsenic ions, which caused a decrease in the current intensity. The experimental optimum working conditions of pH, substrate concentration and potential applied, were established. Under these conditions, repeatability and reproducibility of biosensors were determined, reaching values below 4% in terms of relative standard deviation. The detection limit obtained for arsenic was 1.1 × 10−8 M for Ach/SPCE biosensor. Analysis of the possible effect of the presence of foreign ions in the solution was performed. The method was applied to determine levels of arsenic in spiked tap water samples.Junta de Castilla y León (BU022A07, Q0968272E) and the Ministerio de Ciencia e Innovación (TEC2008-01367/TEC) is gratefully acknowledged

Univariate data analysis versus multivariate approach in liquid chromatography. An application for melamine migration from food contact materials

The aim of this work is focused on the melamine migration from food contact materials (FCMs), considering data obtained from univariate analysis versus that obtained from multivariate approach in liquid chromatography coupled to diode array detector. Plastic food contact materials are made from monomers and additives. Moreover, non-intentionally added substances (NIAS) can be part of the composition of the FCM: raw material impurities or process by-products, inks or adhesives. Any compound present within a FCM can migrate to foodstuff. Specific migration of some substances from plastic FCMs to food/simulant is limited by European legislation in force (Commission Regulation No 10/2011). Quantification of analytes in migration samples through a univariate analysis could lead to erroneous results. As an example, in liquid chromatography NIAS can interfere when coeluting with analytes or when they have close retention time. In that case, an overestimation would happen and the verification of the compliance of the specific migration limit (SML) of a substance would be incorrect. A solution to the problem can be found in the application of a chemometric tool with the second-order advantage, which allows the unequivocal identification of analytes. Specifically, for this work, PARAFAC/ PARAFAC2 decomposition technique along with tensors arranged from HPLC-DAD data of migration (test and kinetics) samples were used for the identification and quantification of melamine. Results of melamine quantity found in migration samples from five types of melaware by means of a multivariate approach were compared to results obtained with a univariate data analysis carried out with values of chromatographic peak area as response. The comparison reveals that in test samples, univariate analysis supposes an overestimation in the quantity of melamine of 30 % on average, with respect of the concentration obtained from the multivariate approach. Besides, in kinetics samples it is remarkable that for one migration cycle the melamine found was 10 times above the one that obtained with PARAFAC decomposition. Summing up, multivariate data analysis of migration samples supposes a great advantage in order to comply with the established regulation about migrants and to decrease the false non-compliant results.The authors thank the Consejería de Educación de la Junta de Castilla y León, Spain for financial support through project BU052P20, cofinanced with FEDER funds. M.M. Arce wish to thank JCyL for her postdoctoral contract through project BU052P20

Kinetic models of migration of melamine and formaldehyde from melamine kitchenware with data of liquid chromatography

European legislation has established a specific migration limit (SML) of 15 mg kg−1 for formaldehyde and 2.5 mg kg−1 for melamine. Formaldehyde resins are used in the manufacture of melamine kitchenware. Formaldehyde is listed in group 1 of the IARC list of carcinogenic compounds. To determine the quantity of formaldehyde and melamine as potential migrants from different types of melamine kitchenware (glass, mug, cutlery, big cup and bowl), a HPLC-DAD method has been implemented. This method is an alternative to the ones proposed in technical guidelines to determine formaldehyde by UV–vis spectrophotometry and melamine by HPLC. The final objective was to fit the migration kinetic curves of these two analytes in melamine kitchenware. After the method was validated, decision limit (CCα) and detection capability (CCβ) were calculated for both analytes, when the probabilities of false positive (α) and false negative (β) were fixed at 0.05; being CCβ 0.269 mg L−1 and 0.311 mg L−1 for melamine and formaldehyde respectively. CCα and CCβ were also calculated at the SML of both analytes. The migration testing were conducted with simulant B (3% acetic acid (w/v) in aqueous solution), the conditions of each exposure being 70 °C for 2 h. The quantities of melamine and formaldehyde found in the third exposure of the total kitchenware analysed were between 0.21 and 1.09 mg L−1 and between 0.55 and 3.86 mg L−1, respectively. Migration kinetic curves were built for each type of kitchenware with the data of sixteen consecutive migration cycles (70 °C each 30 min). The SML for melamine was surpassed in the mug, in the big cup and in the bowl after eleven, thirteen and one cycles, respectively. When more cycles were carried out in the mug, the values of the accumulated quantity of formaldehyde and melamine were 15.30 and 6.79 mg L−1, respectively, after thirty-two cycles. Both concentrations exceeded the corresponding SML.MINECO (AEI/FEDER, UE) and Consejería de Educación de la Junta de Castilla y León through projects CTQ2017-88894-R and BU012P17 respectively (all co-financed with FEDER funds

Determination of cochineal and erythrosine in cherries in syrup in the presence of quenching effect by means of excitation-emission fluorescence data and three-way PARAFAC decomposition

The simultaneous determination of two food colorants (cochineal (E-120) and erythrosine (E-127)) was achieved by means of excitation-emission fluorescence matrices and three-way PARAFAC decomposition together with the use of a calibration set that contained binary mixtures of both analytes. In the measured conditions, the amount of cochineal present in the sample affected the fluorescence signal of erythrosine since cochineal caused a quenching effect in the fluorescence of the other food additive. However, the signal of cochineal was not affected by the presence of erythrosine. A calibration line for erythrosine was built for each different concentration level of cochineal. The slopes of these regressions were different depending on the amount of quencher, whereas the intercepts were statistically equal to 0 at a 95% confidence level. The quantification of erythrosine was possible using the regression “amount of cochineal” versus “the slope of the calibration line for erythrosine”. Using this procedure, the mean of the absolute values of the relative errors in prediction for mixtures of both colorants were 5.86% (n = 10) for cochineal and 4.17% (n = 10) for erythrosine. Both analytes were unequivocally identified by the correlation between the pure spectra and the PARAFAC excitation and emission spectral loadings. Pitted cherries in syrup were analyzed. Cochineal and erythrosine were detected in those cherries at a concentration of 185.05 mg kg−1 and 10.76 mg kg−1, respectively. These concentration values were statistically equal to the ones obtained with a HPLC/DAD method.Spanish MINECO (AEI/FEDER, UE) through projects CTQ2014–53157-R and CTQ2017‐88894‐R and by Junta de Castilla y León through project BU012P1

Optimization of a headspace solid-phase microextraction and gas chromatography/mass spectrometry procedure for the determination of aromatic amines in water and in polyamide spoons

In this work, a headspace solid-phase microextraction and gas chromatography coupledwith mass spectrometry (HS-SPME-GC/MS) method for trace determination of primary aromatic amines was developed. The following analytes were investigated: aniline (A), 4,4′-diaminodiphenylmethane (4,4′-MDA) and 2,4-diaminotoluene (2,4-TDA) using 3-chloro-4-fluoroaniline (3C4FA) and 2-aminobiphenyl (2ABP) as internal standards. Prior to extraction the analytes were derivatized in the aqueous solution by diazotation and subsequent iodination. The derivativeswere extracted byHS-SPME using a PDMS/DVB fiber and analyzed by GC/MS. A D-optimal design was used to study the parameters affecting the HS-SPME procedure and the derivatization step. Two experimental factors at two levels and one factor at three levels were considered: (i) reaction time, (ii) extraction temperature, and (iii) extraction time in the headspace. The interaction between the extraction temperature and extraction time was considered in the proposed model. The loadings in the sample mode estimated by a PARAFAC (parallel factor analysis) decomposition for each analyte were the response used in the design because they are proportional to the amount of analyte extracted. The optimum conditions for the best extraction of the analytes were achieved when the reaction time was 20 min, the extraction temperature was 50 °C and the extraction time was 25 min. The interaction was significant. A calibration based on a PARAFAC decomposition provided the following values of decision limit (CCα): 1.07 μgL−1 for A, 1.23 μg L−1 for 2,4-TDA and 0.83 μg L−1 for 4,4′-MDA for a probability of false positive fixed at 5%. Also, the accuracy (trueness and precision) of the procedurewas assessed. Furthermore, all the analyteswere unequivocally identified. Finally, the method was applied to spiked water samples and polyamide cooking utensils (spoons). 3% (w/v) acetic acid in aqueous solution was used as food simulant for testing migration from polyamide kitchenware. Detectable levels of 4,4′-diaminodiphenylmethane and aniline were found in food simulant from some of the investigated cooking utensils.Ministerio de Economía y Competitividad (CTQ2011-26022) and Junta de Castilla y León (BU108A11-2

Fluorescence determination of cochineal in strawberry jam in the presence of carmoisine as a quencher by means of four-way PARAFAC decomposition

The determination of cochineal (E-120) in strawberry jam was carried out in the presence of carmoisine (E-122) using the four-way PARAFAC decomposition and excitation-emission fluorescence matrices. In the measured conditions, there was no fluorescence signal for carmoisine due to a strong quenching effect and this colorant also led to a decrease of the fluorescence signal of cochineal. The European Union has fixed a maximum residue level, MRL, for cochineal in jam (100 mg kg−1). Therefore, the addition of other food colorant (carmoisine) in the jam could lead to false compliant decisions. The four-way PARAFAC decomposition avoided false compliant decisions caused by the quenching effect. Cochineal was unequivocally identified. Detection capability (CCβ) was 0.72 mg L−1 for probabilities of false positive and false negative fixed at 0.05. Cochineal was detected in the jam (104.63 mg kg−1) above the MRL. This amount was compared with the one obtained using a HPLC/DAD method.Spanish MINECO (AEI/FEDER, UE) through project CTQ2017‐88894-R and by Junta de Castilla y León through project BU012P17 (all co‐financed with European FEDER funds)

Procedure to build a signal transfer set, independent of the target analytes, between a portable fluorimeter based on light-emitting diodes and a master fluorimeter

The need of performing “in situ” analytical determinations together with the availability of high-power deep UV-LEDs have led to the use of fluorescence spectroscopy. However, it is necessary to register excitation-emission matrices (EEM) to obtain three-way data which can be decomposed using parallel factor analysis for enabling the unequivocal identification of the analytes. In this context, the feasibility of transferring EEM between a portable fluorimeter based on LEDs and a master fluorimeter based on a xenon source has been recently reported without losing analytical quality. To build the transfer function, the signals of the same N samples must be recorded in the portable and in the master fluorimeter. In literature, these samples always contained the target analytes so the EEM signal transfer methodology is very limited in practice. Therefore, the challenge is to search for a set of samples whose EEM enable to perform the signal transfer without previously knowing the target analytes. The aim of this work is the design of a procedure to build N mixtures of P fluorophores so the N EEM would be optimal for the signal transfer. Five criteria have been defined a priori to identify the quality of a transfer set made up of N EEM. Then, a procedure has been designed to obtain the n mixtures of the P fluorophores “in silico” using the Pareto front of the optimal solutions and a desirability function to choose the desired N EEM. The procedure has been used to find five mixtures of the three chosen fluorophores for the signal transfer (coumarin 120, DL-Tyrosine and DL-Tryptophan) which are chemically different from the analytes of interest (enrofloxacin and flumequine) and are contained in a different matrix. These two analytes are antibiotics which have maximum residue limits set in the EU legislation in force. The correlation coefficients between the experimental reference spectra and the PARAFAC spectral loadings of the data registered with the master fluorimeter were greater than or equal to 0.999 in all cases. On the other hand, the correlation coefficients obtained with the portable fluorimeter ranged from 0.900 to 0.950 once the procedure was applied to the two antibiotics. Therefore, the unequivocal identification of the analytes was ensured.Spanish MINECO (AEI/FEDER, UE) through project CTQ2017‐88894‐R and by Junta de Castilla y León through project BU012P17 (all co‐financed with European FEDER funds)

Signal transfer with excitation-emission matrices between a portable fluorimeter based on light-emitting diodes and a master fluorimeter

In this work, the transfer of the excitation-emission matrices between a portable fluorimeter based on LEDs and a master fluorimeter based on a xenon source was carried out. Enrofloxacin was the analyte of interest and it was measured alone or in binary mixtures with flumequine (partially overlapped signals) or with ciprofloxacin (fully overlapped signals). The maintenance and transfer of the unequivocal identification of the fluorophores between both instruments are shown. The precision in the determination performed with the portable fluorimeter approximated to that made with the master fluorimeter using this transfer and it did not introduce bias. The correlation coefficients of the calibrations based on PARAFAC using EEM signals were higher than 0.999, whereas the values of the capability of detection ranged from 14.8 to 26.9 μg L−1 for probabilities of false positive and false negative fixed at 0.05. These results contribute to the effort to perform the fluorimetric detection outside the laboratory and to promote the use of databases of fluorescence spectra for the unequivocal identification in remote of fluorophores of interest and/or regulated.Spanish MINECO (AEI/FEDER, UE) through projects CTQ2014-53157-R and CTQ2017‐88894‐R and by Junta de Castilla y León through project BU012P17 (all co‐financed with European FEDER funds

Procedure to explore a ternary mixture diagram to find the appropriate gradient profile in liquid chromatography with fluorescence detector. Application to determine four primary aromatic amines in napkins

The purpose of this work is to develop a tool to search for a gradient profile with ternary or binary mixtures in liquid chromatography, that can provide well-resolved chromatograms in the shortest time for multianalyte analysis. This approach is based exclusively on experimental data and does not require a retention time model of the compounds to be separated. The methodology has been applied for the quantification of four primary aromatic amines (PAAs) using HPLC with fluorescence detector (FLD). Aniline (ANL), 2,4-diaminotoluene (TDA), 4,4 -methylenedianiline (MDA) and 2-aminobiphenyl (ABP) have been selected since their importance in food contact materials (FCM). In order to achieve that, partial least squares (PLS) models have been fitted to relate CMP (control method parameters) and CQA (critical quality attributes). Specifically, PLS models have been fitted using 30 experiments for each one of the four CQA (resolution between peaks and total elution time), considering 33 predictor variables (the composition of the methanol and acetonitrile in the mobile phase and the time of each one of the 11 isocratic segments of the gradient). These models have been used to predict new candidate gradients, and then, some of those predictions (the ones with resolutions above 1.5, in absolute value, and final time lower than 20 min) have been experimentally validated. Detection capability of the method has been evaluated obtaining 1.8, 189.4, 28.8 and 3.0 μg L−1 for ANL, TDA, MDA and ABP, respectively. Finally, the application of chemometric tools like PARAFAC2 allowed the accurate quantification of ANL, TDA, MDA and ABP in paper napkins in the presence of other interfering substances coextracted in the sample preparation process. ANL has been detected in the three napkins analysed in quantities between 33.5 and 619.3 μg L−1, while TDA is present in only two napkins in quantities between 725.9 and 1908 μg L−1. In every case, the amount of PAAs found, exceeded the migration limits established in European regulations.The authors thank the Consejería de Educación de la Junta de Castilla y León for financial support through project BU052P20, cofinanced with FEDER funds. M.M. Arce wish to thank JCyL for her postdoctoral contract through project BU052P20