Functionalization of Screen-Printed Electrodes with Grape Stalk Waste Extract-Assisted Synthesized Silver and Gold Nanoparticles: Perspectives of electrocatalytically Enhanced Determination of Uranyl Ion and Other Heavy Metals Ions

Recently, nanotechnology and nanoparticles (NPs) such as AgNPs and AuNPs have become important in analytical chemistry due to their great potential to improve the performance of electrochemical sensors. In this work, Ag and Au nanoparticles have been synthesized using a green route in which a grape stalk waste extract is used as a reducing agent to obtain metallic nanoparticles. These NPs were used to customize the surface of commercial screen-printed electrodes (SPCNFEs). The spin-coating method was used to modify commercial SPCNFEs under a nitrogen atmosphere. The resulting electrodes were used in a determination study of Cd(II), Pb(II), and U(VI) with differential pulse anodic stripping voltammetry (DPASV). The customized green AgNPs and AuNPs electrodes presented higher sensitivity and electroanalytical performance than the nonmodified SPCNFE. The results showed that the best analytical parameters were obtained with the green, silver nanoparticle SPCNFEs, with a LOD of 0.12 µg L−1 for Pb(II), which is a lower value compared to the most restrictive regulation guidelines. Additionally, the U(VI) ion was successfully determined using the developed G-AgNPs-SPCNFE in spiked tap water, showing comparable results with the ICP-MS techniqu

Customized screen-printed electrodes based on Ag-nanoseeds for enhanced electroanalytical response towards Cd(II), Pb(II) and As(V) in aqueous samples

Electrochemical analysis based on screen-printed electrodes (SPEs) represents a great alternative to conventional analytical methods such as ICP-MS or LC-MS due to their portability, sensitivity, selectivity, and cost-effectiveness. In addition, the functionalization of SPEs with nanomaterials has been reported to provide an enhanced analytical performance. In this regard, silver nanoparticles (AgNPs) were synthesized and appropriately characterized, showing spherical silver nanoseeds (Ag-NS) with a diameter of 12.20 ± 0.04 nm. Using the drop-casting methodology, the synthesized AgNPs were used to modify screen-printed carbon nanofiber electrodes (SPCNFEs). Ag-NS deposition onto the electrode surface was confirmed by scanning electron microscopy (SEM). Furthermore, the analytical response of the modified electrodes (Ag-NS-SPCNFE) was evaluated for the determination of trace Pb(II), Cd(II), and As(V) using differential pulse anodic stripping voltammetry (DPASV), obtaining detection limits of 3.3, 3.7, and 2.6 µg L-1, for Pb(II), Cd(II) and As(V), respectively. Finally, Ag-NS-SPCNFE was tested towards the determination of As(V) in a spiked tap water sample, showing a good agreement with concentrations determined by ICP-MS.Peer ReviewedPostprint (published version

Como usar Atenea en la gestión de grupos en una asignatura de laboratorio de Química

En esta propuesta se presenta la experiencia de utilización del campus virtual ATENEA como herramienta de comunicación y de gestión de la interacción tanto profesorado-alumnado como alumnado-alumnado en la asignatura de Experimentación en Química II de segundo curso de la titulación de Ingeniería Química, que se imparte en la ETSEIB. Atenea ha demostrado ser una herramienta eficaz que ha permitido, durante el curso 2009-10, facilitar la información general y la planificación temporal de todas las actividades de la asignatura, además de gestionar el seguimiento y retroacción de las tareas de los grupos de trabajo cooperativo.Peer Reviewe

Nickel removal from exhausted electroplatting baths by using vegetable wastes

During the last years our research group has been studying the use of industrial vegetable wastes as grape stalks and exhausted coffee to remove metals ions such as Ni(II), Cu(II), Pb(II), Zn(II), Cd(II) or Cr(VI) and Cr(III) in aqueous solution from the point of view to use these wastes as biosorbents in a low cost alternative to activated carbon for wastewater treatment. The optimal experimental conditions for the removal of each of these metal ions in synthetic solutions by using both biosorbents were determined in previous studies . In this work, the performance of grape stalks and exhausted coffee for the removal of nickel ions from an exhausted electroplating bath of a metal finishing industry from Barcelona (Spain) has been investigated. Batch and column experiments were carried out at room temperature by using grape stalk wastes (particle size 0.8-1.0 mm), meanwhile in the case of exhausted coffee, two different particle size ranges were used, 0.25-0.50 mm and 0.50-1.00 mm for batch and column experiments, respectively. Kinetics and equilibrium studies were carried out in batch mode to determine the equilibrium contact time and to obtain the sorption capacity of sorbents. The data in both studies have been treated by using different models. Column experiments were designed to establish the optimal condition for the treatment of the industrial wastewater. The experiments were performed in packed bed up flow columns of different internal diameter and bed depth in order to predict the transport and sorption parameters. In all column experiments the flow rate was around 11 mL h-1. From perspective of process modelling, the dynamic behavior was described in terms of breakthrough curves. The bed depth service time (BDST), Thomas and Yoon Nelson models were used to analyze the experimental data and to determine model parameters. Batch results show that about 1hour was the time needed to reach equilibrium when using grape stalks and around 15 h when using exhausted coffee. In the case of exhausted coffee, the pH solution decreased during the sorption process from initial pH 5,5 to lower pH than the corresponding pHpzc (point zero charge). To avoid this, pH solution was controlled to a constant pH 5,5 and the equilibrium were achieved in 1h. Kinetic data of both sorption processes fit pseudo-second order model, indicating that chemisorption could be rate limiting in the sorption step. Equilibrium data of nickel sorption onto grape stalks and exhausted coffee fit adequately Langmuir model, indicating monolayer coverage. Results showed that maximum sorption capacity of grape stalks (4,8 10-2 mmol/g; 2,84 mg/g) is slightly higher than exhausted coffee (2,9 10-2 mmol/g; 1,70 mg/g). The maximum nickel sorption capacity of both sorbents was reduced to 50% compared to maximum sorption capacity determined using synthetic Ni(II) solutions. Thus, grape stalks and exhausted coffee performance for the removal of Ni(II) from the studied industrial wastewater are negatively affected by the presence of other compounds in the industrial wastewater. In column experiments, the best results were obtained by using 2.8 cm internal diameter columns and bed depth 6 cm and 8 cm for grape stalks and exhausted coffee, respectively. Breakthrough curves were successfully modelled by the proposed columns models. The results obtained demonstrated that grape stalks sorption capacity was higher than exhausted coffee but this one presented a higher sorption rate.Postprint (published version

Direct As(V) Determination Using Screen-Printed Electrodes Modified with Silver Nanoparticles

Carbon-nanofiber-based screen-printed electrodes modified with silver nanoparticles (Ag-NP-SPCNFEs) were tested in a pioneering manner for the direct determination of As(V) at low μg L-1 levels by means of differential pulse anodic stripping voltammetry. Screen-printed electrodes were modified with two different types of Ag-NPs, nanoseeds (NS), and nanoprisms (NPr) and characterized both microscopically and electrochemically. Furthermore, after optimizing the direct voltammetric determination of As(V), the analytical performance of considered sensors was compared for the direct determination of As(V). These results suggest that Ag-NS offer a better analytical response compared to Ag-NPr, with a detection and quantification limit of 0.6 and 1.9 µg L-1, respectively. The proposed methodology was validated using a spiked tap water sample with a very high reproducibility and good agreement with inductively coupled plasma - mass spectrometry (ICP-MS) measurements

Direct As(V) Determination Using Screen-Printed Electrodes Modified with Silver Manoparticles

Carbon-nanofiber-based screen-printed electrodes modified with silver nanoparticles (Ag-NP-SPCNFEs) were tested in a pioneering manner for the direct determination of As(V) at low µg L–1 levels by means of differential pulse anodic stripping voltammetry. Screen-printed electrodes were modified with two different types of Ag-NPs, nanoseeds (NS), and nanoprisms (NPr) and characterized both microscopically and electrochemically. Furthermore, after optimizing the direct voltammetric determination of As(V), the analytical performance of considered sensors was compared for the direct determination of As(V). These results suggest that Ag-NS offer a better analytical response compared to Ag-NPr, with a detection and quantification limit of 0.6 and 1.9 µg L–1, respectively. The proposed methodology was validated using a spiked tap water sample with a very high reproducibility and good agreement with inductively coupled plasma - mass spectrometry (ICP-MS) measurementsPeer ReviewedPostprint (published version

Valorització de residus vegetals procedents de processos industrials com a biosorbents per a l'eliminació d'ions metàl•lics d'afluents aquosos

L’objectiu d’aquest projecte és la valorització de residus vegetals procedents de processos industrials, com són el pinyol d’oliva, rapa del raïm, suro, marro de cafè, etc.,com a biosorbents per a l’eliminació de diferents ions metàl·lics, crom, arsènic, plom, cadmi, coure, níquel, etc., d’afluents aquosos.Peer Reviewe

Strategies for surface modification with Ag-shaped nanoparticles: electrocatalytic enhancement of screen-printed electrodes for the detection of heavy metals

Screen-printed carbon nanofiber electrodes (SPCNFEs) represent an alternative with great acceptance due to their results, as well as their low impact on the environment. In order to improve their performance, in the present work they were modified with silver nanoparticles (Ag-NPs) and electrochemically characterized by using anodic stripping voltammetry. From the Ag-NP synthesis, silver seeds (Ag-NS) and silver nanoprisms (Ag-NPr) were obtained. The Ag-NP formation was confirmed by micrographs, where Ag-NPs with diameters of 12.20 ± 0.04 nm for Ag-NS and 20.40 ± 0.09 nm for Ag-NPr were observed. The electrodes were modified by using three different deposition methods—drop-casting, spin-coating, and in situ approaches—that offer different nanoparticle distribution and electrode modification times. It was observed that the last methodology showed a low amount of Ag-NS deposited on the electrode surface and deep alteration of this surface. Those facts suggest that the in situ synthesis methodology was not appropriate for the determination of heavy metals, and it was discarded. The incorporation of the nanoparticles by spin-coating and drop-casting strategies showed different spatial distribution on the electrode surface, as proved by scanning electron microscopy. The electrodes modified by these strategies were evaluated for the cadmium(II) and lead(II) detection using differential pulse anodic stripping voltammetry, obtaining detection limit values of 2.1 and 2.8 µg·L-1, respectively. The overall results showed that the incorporation route does not directly change the electrocatalytic effect of the nanoparticles, but the shape of these nanoparticles (spherical for seeds and triangular for prisms) has preferential electrocatalytic enhancement over Cd(II) or Pb(II)Postprint (published version

Do Totiviruses of the veil of Flor yeasts provide an evolutionary advantage?

The main objective of this work was to isolate and characterize viruses that infect both Saccharomyces and other Flor veil-forming genera and suggest the possible consequences they can have on the processes of formation of the Flor veil of typical D.O. Jerez-Xèrés-Sherry wines. Results obtained show that different Flor veil yeast strains isolated in Fino wines and in Amontillados presented a great resistance to ethanol and all of them presented infection by Totiviruses. These were identified after the extraction of double-stranded RNA and amplified by multiplex PCR with specific primers for the most common viruses involved in the killer factor. Subsequently, the same strains of both the S. cerevisiae species and Wickerhamomyces anomalus were subjected to an antiviral treatment with ribavirin. After microbiological analysis with Methylene Blue (MB) plates and by rt-PCR, it was determined that most of them did not show killer factor and the viruses involved in it had been correctly eliminated under the treatment with ribavirin. Subsequently, competition and implantation experiments of the treated and untreated yeasts were carried out against their controls. The wines inoculated with yeasts infected by Totiviruses showed to be dominant in all cases

Green synthesis of Ag nanoparticles using grape stalk waste extract for the modification of screen-printed electrodes

The chemical synthesis of silver nanoparticles (Ag-NPs) by using an environmentally friendly methodology for their preparation is presented. Thus, considering that plants possess components that can act as reducing agents and stabilizers in nanoparticles' production, the synthesis of Ag-NPs by using an extract aqueous solution of grape stalk waste as a reducing and capping agent is studied. First, the total polyphenols and reducing sugars contained in the produced extracts at different conditions are characterized. After that, Ag-NPs are synthesized regarding the interaction of Ag ions (from silver nitrate) and the grape stalk extract. The effect of temperature, contact time, extract/metal solution volume ratio and pH solution in the synthesis of metal nanoparticles are also studied. Different sets of nanoparticle samples are characterized by means of Electron Microscopy coupled with Energy Dispersive X-Ray for qualitative chemical identification. Ag-NPs with an average diameter of 27.7 ± 0.6 nm are selected to proof their suitability for sensing purposes. Finally, screen-printed electrodes modified with Ag-NPs are tested for the simultaneous stripping voltammetric determination of Pb(II) and Cd(II). Results indicate good reproducibility, sensitivity and limits of detection around 2.7 µg L−1 for both metal ions