Creación de material docente multimedia interdisciplinar para el desarrollo de un laboratorio virtual de ensayos tecnológicos

EL proyecto general consiste en la creación de una plataforma on-line de un Laboratorio Virtual de Ciencia e Ingeniería de Materiales para los alumnos de Grados en el ámbito de la Ingeniería Industrial de la Universidad de Valladolid centrado en este caso particular en el desarrollo de Ensayos Tecnológicos para el Control de Calidad de Material de interés industrial. Se han llevado a cabo las diferentes fases en las que se ha concretado este proyecto. Estas fases han consistido en la revisión bibliográfica de la temática, en la preparación de probetas para la realización de ensayos de caracterización tecnológico, en la elaboración de material didáctico como manuales de prácticas de laboratorio, en el diseño y elaboración de material adiovisual y en la realización práctica de la plataforma on-line. Par completar el trabajo se han las unidades didácticas de apoyo y como última fase del proyecto se está actualmente incorporando toda la información a la plataforma on-line para unificar el formato con el otros laboratorios de caracterización microestructural y mecánica diseñados por el grupo de trabajo del proyect

Discrimination of milks with a multisensor system based on layer-by-layer films

Producción CientíficaA nanostructured electrochemical bi-sensor system for the analysis of milks has been developed using the layer-by-layer technique. The non-enzymatic sensor [CHI+IL/CuPcS]2, is a layered material containing a negative film of the anionic sulfonated copper phthalocyanine (CuPcS) acting as electrocatalytic material, and a cationic layer containing a mixture of an ionic liquid (IL) (1-butyl-3-methylimidazolium tetrafluoroborate) that enhances the conductivity, and chitosan (CHI), that facilitates the enzyme immobilization. The biosensor ([CHI+IL/CuPcS]2-GAO) results from the immobilization of galactose oxidase on the top of the LbL layers. FTIR, UV–vis, and AFM have confirmed the proposed structure and cyclic voltammetry has demonstrated the amplification caused by the combination of materials in the film. Sensors have been combined to form an electronic tongue for milk analysis. Principal component analysis has revealed the ability of the sensor system to discriminate between milk samples with different lactose content. Using a PLS-1 calibration models, correlations have been found between the voltammetric signals and chemical parameters measured by classical methods. PLS-1 models provide excellent correlations with lactose content. Additional information about other components, such as fats, proteins, and acidity, can also be obtained. The method developed is simple, and the short response time permits its use in assaying milk samples online.Ministerio de Economía, Industria y Competitividad - Fondo Europeo de Desarrollo Regional (project AGL2015-67482-R)Junta de Castilla y Leon - Fondo Europeo de Desarrollo Regional (project VA-011U16)Junta de Castilla y León (grant BOCYL-D-4112015-9

Abnormal magnetic behaviour of powder metallurgy austenitic stainless steels sintered in nitrogen

The magnetic response of AISI 304L and AISI 316L obtained through powder metallurgy and sintered in nitrogen were studied. AISI 304L sintered in nitrogen showed a ferromagnetic behaviour in as-sintered state while AISI 316L was paramagnetic. After solution annealing both were paramagnetic. Magnetic behaviour was analysed by using a vibrating sample magnetometer, a magnetic ferritscope and magnetic etching. A microstructural characterization was performed by means of optical metallography, X-ray diffraction, scanning electron microscopy (SEM) and energy dispersive analysis of X-rays (EDS). Some samples when needed were submitted to aged heat treatments at 675 and 875 °C for 90 min, 4, 6, 8 or 48 h. The main microstructural feature found was the presence of a lamellar constituent formed by nitride precipitates and an interlamellar matrix of austenite and/or ferrite. The abnormal magnetic response was explained based on this.Dirección General de Programas y Transferencia de Conocimiento, Ministerio de Ciencia e Innovación, España, MAT2008-0278

Analysis of musts and wines by means of a bio-electronic tongue based on tyrosinase and glucose oxidase using polypyrrole/gold nanoparticles as the electron mediator

Producción CientíficaA bioelectronic tongue (bioET) based on combinations of enzymes (tyrosinase and glucose oxidase) and polypyrrole (Ppy) or polypyrrole/AuNP (Ppy/AuNP) composites was build up and applied to the analysis and discrimination of musts and wines. Voltammetric responses of the array of sensors demonstrated the effectiveness of polymers as electron mediators and the existence of favorable synergistic effects between Ppy and the AuNPs. Using Principal Component Analysis and Parallel Factor Analysis it was possible to discriminate musts according to the °Brix and TPI (Total Polyphenol Index), and wines according to the alcoholic degree and TPI. Partial Least Squares provided good correlations between the bioET output and traditional chemical parameters. Moreover, Support Vector Machines permitted to predict the TPI and the alcoholic degree of wines, from data provided by the bioET in the corresponding grapes. This result opens the possibility to predict wine characteristics from the beginning of the vinification process.Ministerio de Economía, Industria y Competitividad - Fondo Europeo de Desarrollo Regional (project AGL2015-67482-R)Junta de Castilla y León - Fondo Europeo de Desarrollo Regional (project VA275P18)Junta de Castilla y León (grant BOCYL-D-4112015-9

Promoting laccase sensing activity for catechol detection using LBL assemblies of chitosan/ionic liquid/phthalocyanine as immobilization surfaces

Producción CientíficaThe performance of electrochemical laccase-based biosensors can be improved by immobilizing the enzyme on composite Layer-by-Layer (LbL) supports in which materials with complementary functions are combined. LbL films are formed by layers combining an electrocatalytic material which favors electron transfer (sulfonated copper phthalocyanine, CuPcS(−)), an ionic liquid which enhances the electrical conductivity of the layers (1-butyl-3-methylimidazolium tetrafluoroborate, IL(+)) and a material able to promote enzyme immobilization (chitosan, CHI(+)). Composite films with different structures have been demonstrated to be efficient electrocatalysts, producing an increase in the magnitude of the responses towards catechol. The most intense and reproducible electrocatalytic effect was observed when a layer of the CuPcS(−) was placed on top of a layer formed by a mixture of CHI(+) + IL(+) to obtain [CHI(+) + IL(+)|CuPcS(−)]2 films. Biosensors with laccase immobilized on the surface of the LbL layers [CHI(+) + IL(+)|CuPcS(−)]2|Lac showed mediated electron transfer between the redox enzyme and the film and a reproducibility of device-to-device performance of 4.1%. The amperometric biosensor showed a sensitivity of 0.237 A·M−1 and a linear detection range from 2.4 μM to 26 μM for catechol. The excellent Limit of detection (LOD) of 8.96·10−10 M (3·σ /m) is one order of magnitude lower than that obtained in similar studies. A Michaelis-Menten constant of 3.16 μM confirms excellent enzyme-substrate affinity.Ministerio de Economía, Industria y Competitividad - Fondo Europeo de Desarrollo Regional (projects AGL2015-67482-R and RTI2018_097990-B-100)Junta de Castilla y León - Fondo Europeo de Desarrollo Regional (project VA275P18

Polymeric foams as the matrix of voltammetric sensors for the detection of catechol, hydroquinone, and their mixtures

Producción CientíficaPorous electrodes based on polymethylmethacrylate and graphite foams (PMMA_G_F) have been developed and characterized. Such devices have been successfully used as voltammetric sensors to analyze catechol, hydroquinone, and their mixtures. The presence of pores induces important changes in the oxidation/reduction mechanism of catechol and hydroquinone with respect to the sensing properties observed in nonfoamed PMMA_graphite electrodes (PMMA_G). The electropolymerization processes of catechol or hydroquinone at the electrode surface observed using PMMA_G do not occur at the surface of the foamed PMM_G_F. In addition, the limits of detection observed in foamed electrodes are one order of magnitude lower than the observed in the nonfoamed electrodes. Moreover, foamed electrodes can be used to detect simultaneously both isomers and a remarkable increase in the electrocatalytic properties shown by the foamed samples, produces a decrease in the oxidation potential peak of catechol in presence of hydroquinone, from +0.7 V to +0.3 V. Peak currents increased linearly with concentration of catechol in presence of hydroquinone over the range of 0.37·10−3 M to 1.69·10−3 M with a limit of detection (LOD) of 0.27 mM. These effects demonstrate the advantages obtained by increasing the active surface by means of porous structures.Ministerio de Economía, Industria y Competitividad - Fondo Europeo de Desarrollo Regional (project AGL2015-67482-R)Junta de Castilla y Leon - Fondo Europeo de Desarrollo Regional (project VA-011U16

Electrochemical sensors modified with combinations of sulfur containing phthalocyanines and capped gold nanoparticles: A study of the influence of the nature of the interaction between sensing materials

Producción CientíficaVoltametric sensors formed by the combination of a sulfur-substituted zinc phthalocyanine (ZnPcRS) and gold nanoparticles capped with tetraoctylammonium bromide (AuNPtOcBr) have been developed. The influence of the nature of the interaction between both components in the response towards catechol has been evaluated. Electrodes modified with a mixture of nanoparticles and phthalocyanine (AuNPtOcBr/ZnPcRS) show an increase in the intensity of the peak associated with the reduction of catechol. Electrodes modified with a covalent adduct-both component are linked through a thioether bond-(AuNPtOcBr-S-ZnPcR), show an increase in the intensity of the oxidation peak. Voltammograms registered at increasing scan rates show that charge transfer coefficients are different in both types of electrodes confirming that the kinetics of the electrochemical reaction is influenced by the nature of the interaction between both electrocatalytic materials. The limits of detection attained are 0.9 × 10−6 mol∙L−1 for the electrode modified with the mixture AuNPtOcBr/ZnPcRS and 1.3 × 10−7 mol∙L−1 for the electrode modified with the covalent adduct AuNPtOcBr-S-ZnPcR. These results indicate that the establishment of covalent bonds between nanoparticles and phthalocyanines can be a good strategy to obtain sensors with enhanced performance, improving the charge transfer rate and the detection limits of voltammetric sensors.Ministerio de Economía, Industria y Competitividad - Fondo Europeo de Desarrollo Regional (projects RTI2018-097990-B-I00 / CTQ2017-87102-R)Junta de Castilla y Leon - Fondo Europeo de Desarrollo Regional (project VA275P18

Biosensors Platform Based on Chitosan/AuNPs/Phthalocyanine Composite Films for the Electrochemical Detection of Catechol. The Role of the Surface Structure

Producción CientíficaBiosensor platforms consisting of layer by layer films combining materials with different functionalities have been developed and used to obtain improved catechol biosensors. Tyrosinase (Tyr) or laccase (Lac) were deposited onto LbL films formed by layers of a cationic linker (chitosan, CHI) alternating with layers of anionic electrocatalytic materials (sulfonated copper phthalocyanine, CuPcS or gold nanoparticles, AuNP). Films with different layer structures were successfully formed. Characterization of surface roughness and porosity was carried out using AFM. Electrochemical responses towards catechol showed that the LbL composites efficiently improved the electron transfer path between Tyr or Lac and the electrode surface, producing an increase in the intensity over the response in the absence of the LbL platform. LbL structures with higher roughness and pore size facilitated the diffusion of catechol, resulting in lower LODs. The [(CHI)-(AuNP)-(CHI)-(CuPcS)]2-Tyr showed an LOD of 8.55∙10−4 μM, which was one order of magnitude lower than the 9.55·10−3 µM obtained with [(CHI)-(CuPcS)-(CHI)-(AuNP)]2-Tyr, and two orders of magnitude lower than the obtained with other nanostructured platforms. It can be concluded that the combination of adequate materials with complementary activity and the control of the structure of the platform is an excellent strategy to obtain biosensors with improved performances.Ministerio de Ciencia, Innovación y Universidades - Fondo Europeo de Desarrollo Regional (project RTI2018-097990-B-100)Junta de Castilla y Leon - Fondo Europeo de Desarrollo Regional (project VA275P18)Infraestructuras Red de Castilla y León (grant UVA01

Analysis of red wines using an electronic tongue and infrared spectroscopy. Correlations with phenolic content and color parameters

Producción CientíficaThe objective of this work was to develop a methodology based on multiparametric methods (FTIR and a voltammetric e–tongue based on SPE) to evaluate simultaneously fourteen parameters related to the phenolic content of red wines. Eight types of Spanish red wines, elaborated with different grape varieties from different regions and with different aging, were analyzed with both systems. Input variables used for multivariate analysis were extracted from FTIR spectra and voltammograms using the kernel method. PCA analysis could discriminate wines according to their phenolic content with PC1, PC2 and PC3 explaining the 99.8% of the total variance between the samples for FTIR analysis and 85.8% for the e-tongue analysis. PLS calculations were used to establish regression models with phenolic content parameters measured by UV–Vis spectroscopy (TPI, Folin-Ciocalteu, CIELab and Glories) with high correlation coefficients (R2 > 0.85), and low RMSEs (<3.0) and number of factors (<4). Both, PCA and PLS, were carried out using the full cross validation method. As time is a critical factor in the food industry, the main advantage of these multivariate techniques is their capability to evaluate many parameters in a single experiment and in shorter time than using independent classical techniques.Ministerio de Educación y Formación Profesional (project RTI2018-097990-B-I00)Junta de Castilla y Leon (grants VA275P18 and BOCYL-D-24112015-9

Improving the performance of electrochemical sensors by means of synergy. Combinations of gold nanoparticles and phthalocyanines

Producción CientíficaVoltammetric sensors chemically modified with combinations of two electrocatalytic materials: tetraoctylammonium bromide capped gold nanoparticles (AuNPNBr) and a sulphur containing zinc phthalocyanine derivative (ZnPcRS) are reported. The electrocatalytic effects in the detection of catechol have been analyzed in sensors obtained by direct mixing (AuNPNBr/ZnPcRS) and in sensors modified with an adduct where both components are linked covalently (AuNPNBr-S-ZnPcR). Results demonstrate that the nature of the interaction between both components modifies the electrocatalytic properties. The AuNPNBr/ZnPcRS mixture improves the electron transfer rate of the catechol reduction, with limits of detection of 10−6 M. The covalent adduct AuNPNBr-S-ZnPcR enhances the response rate of the oxidation of the catechol with limits of detection of 10−7 M.Ministerio de Economía y Empresa-FEDER (AGL2015-67482-R)Junta de Castilla y Leon - FEDER (VA-032U13)Junta de Castilla y Leon, (grant BOCYL-D-4112015-9