An Embedded-Sensor Approach for Concrete Resistivity Measurement in On-Site Corrosion Monitoring: Cell Constants Determination

[EN] The concrete electrical resistivity is a prominent parameter in structural health monitoring, since, along with corrosion potential, it provides relevant qualitative diagnosis of the reinforcement corrosion. This study proposes a simple expression to reliable determine resistivity from the concrete electrical resistance (R-E) provided by the corrosion sensor of the Integrated Network of Sensors for Smart Corrosion Monitoring (INESSCOM) we have developed. The novelty here is that distinct from common resistivity sensors, the cell constants obtained by the proposed expression are intended to be valid for any sensor implementation scenario. This was ensured by studying most significant geometrical features of the sensor in a wide set of calibration solutions. This embedded-sensor approach is intended to be applicable for R-E measurements obtained both using potential step voltammetry (PSV, used in the INESSCOM sensor for corrosion rate measurement) and alternating current methods. In this regard, we present a simple protocol to reliably determine R-E, and therefore resistivity, from PSV measurements. It consists in adding a very short potentiostatic pulse to the original technique. In this way, we are able to easy monitor resistivity along with corrosion rate through a single sensor, an advantage which is not usual in structural health monitoring.This research was funded by the pre-doctoral scholarship granted to Jose Enrique Ramon Zamora by the Spanish Ministry of Science and Innovation, grant number FPU13/00911. Funding was also provided by the Spanish Ministry of Economy and Competitiveness under the national program for research, development and innovation geared to societal challenges; project number BIA2016-78460-C3-3-R. The research activity reported in this paper has been partially possible thanks to the project Voltammetric Electronic Tongue for Durability Control in Concrete funded by the Universitat Politecnica de Valencia, project number SP20180245.Ramón, JE.; Martínez, I.; Gandía-Romero, JM.; Soto Camino, J. (2021). An Embedded-Sensor Approach for Concrete Resistivity Measurement in On-Site Corrosion Monitoring: Cell Constants Determination. Sensors. 21(7):1-23. https://doi.org/10.3390/s21072481S12321

Monitoring honey adulteration with sugar syrups using an automatic pulse voltammetric electronic tongue

[EN] The new tendency to detect adulterated honey is the development of affordable analytical equipment that is in-line and manageable, enabling rapid on site screening. Therefore, the aim of this work was to apply an electronic tongue based on potential multistep pulse voltammetry, in combination with multivariate statistical techniques to detect and quantify syrup in honey. Pure monofloral honey (heather, orange blossom and sunflower), syrup (rice, barley and corn), and samples simulating adulterated honey with different percentages of syrup (2.5, 5, 10, 20 and 40) were evaluated. An automatic, electrochemical system for cleaning and polishing the electronic tongue sensors (Ir, Rh, Pt, Au) significantly improved the repeatability and accuracy of the measurements. PCA analysis showed that the proposed methodology is able to distinguish between types of pure honey and syrup, and their different levels of adulterants. A subsequent PLS analysis successfully predicted the level of the adulterants in each honey, achieving good correlations considering the adjusting parameters. The best results being for sunflower honey adulterated with corn syrup and heather honey with barley syrup (r2 ¿ 0.997), and heather with corn (r2 ¿ 0.994) whereas the weakest was found for heather honey adulterated with brown rice syrup (r2 ¿ 0.763) and orange blossom honey with corn syrup (r2 ¿ 0.879). The measurement system here proposed could be a very quick and effective option for the honey packaging sector with the finality of providing information about a characteristic as important as the adulteration of honey.This study forms part of the projects funded by the "Agencia Estatal de Investigacion" (AGL2016-77702-R) and by the "Generalitat Valenciana" (AICO/2015/104) of Spain, for which the authors are grateful.Sobrino-Gregorio, L.; Bataller Prats, R.; Soto Camino, J.; Escriche Roberto, MI. (2018). Monitoring honey adulteration with sugar syrups using an automatic pulse voltammetric electronic tongue. Food Control. 91:254-260. https://doi.org/10.1016/j.foodcont.2018.04.003S2542609

Influence of hydrated lime on the chloride-induced reinforcement corrosion in eco-efficient concretes made with high-volume fly ash

[EN] The main objective of this study was to analyze the influence that the addition of finely ground hydrated lime has on chloride-induced reinforcement corrosion in eco-efficient concrete made with 50% cement replacement by fly ash. Six tests were carried out: mercury intrusion porosimetry, chloride migration, accelerated chloride penetration, electrical resistivity, and corrosion rate. The results show that the addition of 10¿20% of lime to fly ash concrete did not affect its resistance to chloride penetration. However, the cementitious matrix density is increased by the pozzolanic reaction between the fly ash and added lime. As a result, the porosity and the electrical resistivity improved (of the order of 10% and 40%, respectively), giving rise to a lower corrosion rate (iCORR) of the rebars and, therefore, an increase in durability. In fact, after subjecting specimens to wetting¿drying cycles in a 0.5 M sodium chloride solution for 630 days, corrosion is considered negligible in fly ash concrete with 10% or 20% lime (iCORR less than 0.2 µA/cm2), while in fly ash concrete without lime, corrosion was low (iCORR of the order of 0.3 µA/cm2) and in the reference concrete made with Portland cement, only the corrosion was high (iCORR between 2 and 3 µA/cm2).This research was funded by MINISTERIO DE ECONOMIA Y COMPETITIVIDAD, grant number MAT2012-38429-C04-04.Valcuende Payá, MO.; Calabuig Pastor, R.; Martínez-Ibernón, A.; Soto Camino, J. (2020). Influence of hydrated lime on the chloride-induced reinforcement corrosion in eco-efficient concretes made with high-volume fly ash. Materials. 13(22):1-16. https://doi.org/10.3390/ma13225135S1161322Isaia, G. C., & Gastaldini, A. L. G. (2009). Concrete sustainability with very high amount of fly ash and slag. Revista IBRACON de Estruturas e Materiais, 2(3), 244-253. doi:10.1590/s1983-41952009000300003Golewski, G. L. (2018). Green concrete composite incorporating fly ash with high strength and fracture toughness. Journal of Cleaner Production, 172, 218-226. doi:10.1016/j.jclepro.2017.10.065Hanehara, S., Tomosawa, F., Kobayakawa, M., & Hwang, K. (2001). Effects of water/powder ratio, mixing ratio of fly ash, and curing temperature on pozzolanic reaction of fly ash in cement paste. Cement and Concrete Research, 31(1), 31-39. doi:10.1016/s0008-8846(00)00441-5Deschner, F., Winnefeld, F., Lothenbach, B., Seufert, S., Schwesig, P., Dittrich, S., … Neubauer, J. (2012). Hydration of Portland cement with high replacement by siliceous fly ash. Cement and Concrete Research, 42(10), 1389-1400. doi:10.1016/j.cemconres.2012.06.009Isaia, G. ., Gastaldini, A. L. ., & Moraes, R. (2003). Physical and pozzolanic action of mineral additions on the mechanical strength of high-performance concrete. Cement and Concrete Composites, 25(1), 69-76. doi:10.1016/s0958-9465(01)00057-9Simčič, T., Pejovnik, S., De Schutter, G., & Bosiljkov, V. B. (2015). Chloride ion penetration into fly ash modified concrete during wetting–drying cycles. Construction and Building Materials, 93, 1216-1223. doi:10.1016/j.conbuildmat.2015.04.033Thomas, M. D. A., Hooton, R. D., Scott, A., & Zibara, H. (2012). The effect of supplementary cementitious materials on chloride binding in hardened cement paste. Cement and Concrete Research, 42(1), 1-7. doi:10.1016/j.cemconres.2011.01.001Delagrave, A., Marchand, J., Ollivier, J.-P., Julien, S., & Hazrati, K. (1997). Chloride binding capacity of various hydrated cement paste systems. Advanced Cement Based Materials, 6(1), 28-35. doi:10.1016/s1065-7355(97)90003-1Chalee, W., Ausapanit, P., & Jaturapitakkul, C. (2010). Utilization of fly ash concrete in marine environment for long term design life analysis. Materials & Design, 31(3), 1242-1249. doi:10.1016/j.matdes.2009.09.024Lollini, F., Redaelli, E., & Bertolini, L. (2015). Investigation on the effect of supplementary cementitious materials on the critical chloride threshold of steel in concrete. Materials and Structures, 49(10), 4147-4165. doi:10.1617/s11527-015-0778-0Baroghel-Bouny, V., Kinomura, K., Thiery, M., & Moscardelli, S. (2011). Easy assessment of durability indicators for service life prediction or quality control of concretes with high volumes of supplementary cementitious materials. Cement and Concrete Composites, 33(8), 832-847. doi:10.1016/j.cemconcomp.2011.04.007Wongkeo, W., Thongsanitgarn, P., & Chaipanich, A. (2012). Compressive strength and drying shrinkage of fly ash-bottom ash-silica fume multi-blended cement mortars. Materials & Design (1980-2015), 36, 655-662. doi:10.1016/j.matdes.2011.11.043Poon, C. S., Lam, L., & Wong, Y. L. (2000). A study on high strength concrete prepared with large volumes of low calcium fly ash. Cement and Concrete Research, 30(3), 447-455. doi:10.1016/s0008-8846(99)00271-9Garcés, P., Andión, L. G., Zornoza, E., Bonilla, M., & Payá, J. (2010). The effect of processed fly ashes on the durability and the corrosion of steel rebars embedded in cement–modified fly ash mortars. Cement and Concrete Composites, 32(3), 204-210. doi:10.1016/j.cemconcomp.2009.11.006Ghafoori, N., Najimi, M., Diawara, H., & Islam, M. S. (2015). Effects of class F fly ash on sulfate resistance of Type V Portland cement concretes under continuous and interrupted sulfate exposures. Construction and Building Materials, 78, 85-91. doi:10.1016/j.conbuildmat.2015.01.004Han, C., Shen, W., Ji, X., Wang, Z., Ding, Q., Xu, G., … Tang, X. (2018). Behavior of high performance concrete pastes with different mineral admixtures in simulated seawater environment. Construction and Building Materials, 187, 426-438. doi:10.1016/j.conbuildmat.2018.07.196Zuquan, J., Xia, Z., Tiejun, Z., & Jianqing, L. (2018). Chloride ions transportation behavior and binding capacity of concrete exposed to different marine corrosion zones. Construction and Building Materials, 177, 170-183. doi:10.1016/j.conbuildmat.2018.05.120Cheewaket, T., Jaturapitakkul, C., & Chalee, W. (2010). Long term performance of chloride binding capacity in fly ash concrete in a marine environment. Construction and Building Materials, 24(8), 1352-1357. doi:10.1016/j.conbuildmat.2009.12.039Fanghui, H., Qiang, W., & Jingjing, F. (2015). The differences among the roles of ground fly ash in the paste, mortar and concrete. Construction and Building Materials, 93, 172-179. doi:10.1016/j.conbuildmat.2015.05.117Alaka, H. A., & Oyedele, L. O. (2016). High volume fly ash concrete: The practical impact of using superabundant dose of high range water reducer. Journal of Building Engineering, 8, 81-90. doi:10.1016/j.jobe.2016.09.008Huang, Q., Zhu, X., Liu, D., Zhao, L., & Zhao, M. (2021). Modification of water absorption and pore structure of high-volume fly ash cement pastes by incorporating nanosilica. Journal of Building Engineering, 33, 101638. doi:10.1016/j.jobe.2020.101638Anjos, M. A. S., Camões, A., Campos, P., Azeredo, G. A., & Ferreira, R. L. S. (2020). Effect of high volume fly ash and metakaolin with and without hydrated lime on the properties of self-compacting concrete. Journal of Building Engineering, 27, 100985. doi:10.1016/j.jobe.2019.100985Herath, C., Gunasekara, C., Law, D. W., & Setunge, S. (2020). Performance of high volume fly ash concrete incorporating additives: A systematic literature review. Construction and Building Materials, 258, 120606. doi:10.1016/j.conbuildmat.2020.120606Lorca, P., Calabuig, R., Benlloch, J., Soriano, L., & Payá, J. (2014). Microconcrete with partial replacement of Portland cement by fly ash and hydrated lime addition. Materials & Design, 64, 535-541. doi:10.1016/j.matdes.2014.08.022Panesar, D. K., & Zhang, R. (2020). Performance comparison of cement replacing materials in concrete: Limestone fillers and supplementary cementing materials – A review. Construction and Building Materials, 251, 118866. doi:10.1016/j.conbuildmat.2020.118866Baert, G., Poppe, A.-M., & De Belie, N. (2008). Strength and durability of high-volume fly ash concrete. Structural Concrete, 9(2), 101-108. doi:10.1680/stco.2008.9.2.101Lammertijn, S., & De Belie, N. (2008). Porosity, gas permeability, carbonation and their interaction in high-volume fly ash concrete. Magazine of Concrete Research, 60(7), 535-545. doi:10.1680/macr.2008.60.7.535Bouzoubaâ, N., Bilodeau, A., Tamtsia, B., & Foo, S. (2010). Carbonation of fly ash concrete: laboratory and field data. Canadian Journal of Civil Engineering, 37(12), 1535-1549. doi:10.1139/l10-081Zhang, Y. M., Sun, W., & Yan, H. D. (2000). Hydration of high-volume fly ash cement pastes. Cement and Concrete Composites, 22(6), 445-452. doi:10.1016/s0958-9465(00)00044-5Zhao, Q., He, X., Zhang, J., & Jiang, J. (2016). Long-age wet curing effect on performance of carbonation resistance of fly ash concrete. Construction and Building Materials, 127, 577-587. doi:10.1016/j.conbuildmat.2016.10.065Barbhuiya, S. A., Gbagbo, J. K., Russell, M. I., & Basheer, P. A. M. (2009). Properties of fly ash concrete modified with hydrated lime and silica fume. Construction and Building Materials, 23(10), 3233-3239. doi:10.1016/j.conbuildmat.2009.06.001Filho, J. H., Medeiros, M. H. F., Pereira, E., Helene, P., & Isaia, G. C. (2013). High-Volume Fly Ash Concrete with and without Hydrated Lime: Chloride Diffusion Coefficient from Accelerated Test. Journal of Materials in Civil Engineering, 25(3), 411-418. doi:10.1061/(asce)mt.1943-5533.0000596Kumar, M., Singh, S. K., & Singh, N. P. (2012). Heat evolution during the hydration of Portland cement in the presence of fly ash, calcium hydroxide and super plasticizer. Thermochimica Acta, 548, 27-32. doi:10.1016/j.tca.2012.08.028Gunasekara, C., Sandanayake, M., Zhou, Z., Law, D. W., & Setunge, S. (2020). Effect of nano-silica addition into high volume fly ash–hydrated lime blended concrete. Construction and Building Materials, 253, 119205. doi:10.1016/j.conbuildmat.2020.119205Mohammed, M. E., Al-Shathr, B. S., & al-Attar, T. S. (2020). Effect of incorporating hydrated lime on strength gain of high-volume fly ash lightweight concrete. IOP Conference Series: Materials Science and Engineering, 737, 012058. doi:10.1088/1757-899x/737/1/012058Bentz, D. P. (2014). Activation energies of high-volume fly ash ternary blends: Hydration and setting. Cement and Concrete Composites, 53, 214-223. doi:10.1016/j.cemconcomp.2014.06.018Gandía-Romero, J. M., Ramón, J. E., Bataller, R., Palací, D. G., Valcuende, M., & Soto, J. (2016). Influence of the area and distance between electrodes on resistivity measurements of concrete. Materials and Structures, 50(1). doi:10.1617/s11527-016-0925-2Ahmad, S. (2003). Reinforcement corrosion in concrete structures, its monitoring and service life prediction––a review. Cement and Concrete Composites, 25(4-5), 459-471. doi:10.1016/s0958-9465(02)00086-0Matos, P. R. de, Sakata, R. D., & Prudêncio, L. R. (2019). Eco-efficient low binder high-performance self-compacting concretes. Construction and Building Materials, 225, 941-955. doi:10.1016/j.conbuildmat.2019.07.254Hornbostel, K., Larsen, C. K., & Geiker, M. R. (2013). Relationship between concrete resistivity and corrosion rate – A literature review. Cement and Concrete Composites, 39, 60-72. doi:10.1016/j.cemconcomp.2013.03.019Shi, C. (2004). Effect of mixing proportions of concrete on its electrical conductivity and the rapid chloride permeability test (ASTM C1202 or ASSHTO T277) results. Cement and Concrete Research, 34(3), 537-545. doi:10.1016/j.cemconres.2003.09.007Li, S., & Roy, D. M. (1986). Investigation of relations between porosity, pore structure, and C1− diffusion of fly ash and blended cement pastes. Cement and Concrete Research, 16(5), 749-759. doi:10.1016/0008-8846(86)90049-9Ngala, V., Page, C., Parrott, L., & Yu, S. (1995). Diffusion in cementitious materials: II, further investigations of chloride and oxygen diffusion in well-cured OPC and OPC/30%PFA pastes. Cement and Concrete Research, 25(4), 819-826. doi:10.1016/0008-8846(95)00072-kZhang, T., & Gjørv, O. E. (1996). Diffusion behavior of chloride ions in concrete. Cement and Concrete Research, 26(6), 907-917. doi:10.1016/0008-8846(96)00069-5Amiri, O., Aı̈t-Mokhtar, A., Dumargue, P., & Touchard, G. (2001). Electrochemical modelling of chloride migration in cement based materials. Electrochimica Acta, 46(9), 1267-1275. doi:10.1016/s0013-4686(00)00717-9Shehata, M. H., Thomas, M. D. A., & Bleszynski, R. F. (1999). The effects of fly ash composition on the chemistry of pore solution in hydrated cement pastes. Cement and Concrete Research, 29(12), 1915-1920. doi:10.1016/s0008-8846(99)00190-8Alonso, M. C., & Sanchez, M. (2009). Analysis of the variability of chloride threshold values in the literature. Materials and Corrosion, 60(8), 631-637. doi:10.1002/maco.20090529

Stainless Steel Voltammetric Sensor to Monitor Variations in Oxygen and Humidity Availability in Reinforcement Concrete Structures

[EN] The present work presents the results obtained with a stainless steel (SS) voltammetric sensor to detect variations in humidity (H2O) and oxygen (O2) availability in concretes. First, studies in solution were run by preparing several solutions to represent the different conditions that can be found in concrete pores. Second, the sensor's response was studied by varying O2 availability by argon or synthetic air bubbling. Then concrete conditions with different degrees of carbonation were simulated using solutions with a pH between 13 and 8.45. After characterization in solution, a study by means of concrete samples with several water/cement ratios (0.6, 0.5 and 0.4) was performed, in which sensors were embedded and studied under different O2 and H2O saturation conditions. The obtained results revealed that with the voltagram, it is possible to evaluate O2 availability variation from the slopes of the lines identified logarithmically in the voltagram for the obtained cathodic sweeping. All the results obtained with the sensor were correlated/validated by standard assays to characterize porosity in hardened concretes.The authors would like to express their gratitude to the Spanish Ministry of Science and Innovation for the pre-doctoral scholarship granted to Ana Martinez Ibernon (FPU 16/00723). To the Universitat Politecnica de Valencia for the financial support in the project "Ayudas a Primeros Proyectos de Investigacion (PAID-06-18): Lengua Electronica Voltametrica para el control de durabilidad en hormigones, SP20180245"Martínez-Ibernón, A.; Lliso-Ferrando, JR.; Gandía-Romero, JM.; Soto Camino, J. (2021). Stainless Steel Voltammetric Sensor to Monitor Variations in Oxygen and Humidity Availability in Reinforcement Concrete Structures. Sensors. 21(8):1-21. https://doi.org/10.3390/s21082851S12121

Antioxidant activity and physicochemical parameters for the differentiation of honey using a potentiometric electronic tongue

[EN] BACKGROUND: This work evaluates the capacity of a potentiometric electronic tongue to differentiate between types of honey (orange blossom, rosemary, thyme, sunflower, winter savory and honeydew honey) according to their antioxidant level. The classical procedures used to evaluate the antioxidant potential of honey are inappropriate for in situ monitoring on reception of batches of raw honey in the packaging industry. They are also destructive, time-consuming and very tedious, requiring highly expert analysts and specialised equipment. RESULTS: The electronic tongue system made with Ag, Ni, Co, Cu and Au was able to not only differentiate between types of honey but also to predict their total antioxidant capacity. The discrimination ability of the system was proved by means of a fuzzy ARTMAP type ANN, with 100% classification success. A prediction multiple linear regression model showed that the best correlation coefficientwas for antioxidant activity (0.9666), then for electrical conductivity (0.8959) and to a lesser extent for aw, moisture and colour. CONCLUSION: The proposed measurement system could be a quick, easy option for the honey packaging sector to provide continuous in-line information about a characteristic as important as the antioxidant level. © 2016 Society of Chemical IndustryThe authors thank the Generalitat Valenciana (Spain) and the Spanish Government for funding the projects AICO/2015/104 and (MAT2015-64139-C4-3-R), respectively.Juan Borrás, MDS.; Soto Camino, J.; Gil Sánchez, L.; Pascual-Maté, A.; Escriche Roberto, MI. (2017). Antioxidant activity and physicochemical parameters for the differentiation of honey using a potentiometric electronic tongue. Journal of the Science of Food and Agriculture. 97(7):2215-2222. https://doi.org/10.1002/jsfa.8031S2215222297

Improvement of a pesticide immunosensor performance using site-directed antibody immobilisation and carbon nanotubes

The potential toxicity of pesticide residues in drinking water has meant a rigid regulation for the appearance of these pollutants. Thus, in this work, we developed a new immunosensor for atrazine detection. We focused on the optimisation of the antibody immobilisation method on sensor surface for the enhancement of the biosensor sensitivity. First, with site-directed immobilisation of rabbit anti-atrazine antibodies using goat anti-rabbit immunoglobulin, a detection limit of 0.5 ng/mL was obtained. This value is 20 times lower than the detection limit obtained with non-oriented antibodies. The second way to improve immunosensor sensitivity consisted of the addition of carbon nanotubes (CNT). As result of using these CNT, detection limit has been improved again from 0.5 ng/mL to 100 pg/mL.This work was financially supported by the PCI cooperation project between Spain and Tunisia.Marrakchi, M.; Helali, S.; Soto Camino, J.; González Martínez, MÁ.; Abdelghani, A.; Hamdi, M. (2013). Improvement of a pesticide immunosensor performance using site-directed antibody immobilisation and carbon nanotubes. International Journal of Nanotechnology. 10:496-507. doi:10.1504/IJNT.2013.053519S4965071

Corrosion resistance of ultra-high performance fibre- reinforced concrete

[EN] The corrosion resistance of ultra-high performance concrete (UH) made with different fibre contents and under distinct curing conditions was studied. No signs of carbonation were observed after 1 year of accelerated carbonation testing (3% CO2). The fibreless UHs¿ electrical resistivity was above 5000 ¿·m, although these values were 2-fold higher than a UH with 1% fibres and approximately 5-fold higher than a UH with 2% fibres. Concrete resistance to chloride penetration was also extremely high (the diffusion coefficient equalled 1.3·10¿13 m2/s) and curing temperatures of 60 °C or 90 °C improved even more these properties, while lack of curing made them slightly worse. Given these excellent properties, the corrosion rate in specimens submerged in chloride solution for 1 year was negligible (iCORR from 0.007 to 0.025 µA/cm2). These values remained stable with time, unlike the 50 MPa concrete at 2 months when iCORR starting to increase and was 12-fold higher after 1 year. The time estimated for corrosion onset in UH is on average about 150-fold higher than that of 50 MPa.Authors thank to the Spanish Government the financial support of project BIA2016-78460-C3-3-R and to the European Union¿s Horizon 2020 the financial support of ReSHEALience project (Grant Agreement No. 760824). Furthermore, authors would like to express their gratitude for the support of the Universitat Politecnica de Valencia. Funding for open access charge: CRUE-Universitat Politecnica de Valencia. The predoctoral scholarship granted to Josep Ramon Lliso Ferrando within the program ¿Formacion de Personal Investigador¿ from the Universitat Politecnica de Valencia (FPI-UPV-2018) is also gratefully acknowledged.Valcuende Payá, MO.; Lliso-Ferrando, JR.; Ramón Zamora, JE.; Soto Camino, J. (2021). Corrosion resistance of ultra-high performance fibre- reinforced concrete. Construction and Building Materials. 306:1-10. https://doi.org/10.1016/j.conbuildmat.2021.124914S11030

Using an automatic pulse voltammetric electronic tongue to verify the origin of honey from Spain, Honduras, and Mozambique

[EN] BACKGROUND: The growing need to classify the origin of honey in a simple way is leading to the development of affordable analytical equipment that is in-line and manageable, enabling rapid on-site screening. The aim of this work was therefore to evaluate whether an electronic tongue (made of four metallic electrodes: Ir, Rh, Pt, Au), based on potential multistep pulse voltammetry with electrochemical polishing, is able to differentiate between honey samples from Spain, Honduras, and Mozambique. RESULTS: It was demonstrated, for the first time, that automatic pulse voltammetry, in combination with principal component analysis (PCA) statistical analysis, was able to differentiate honey samples from these three countries. A partial least squares (PLS) analysis predicted the level of certain physicochemical parameters, the best results being for conductivity and moisture with correlation coefficients of 0.948 and 0.879, whereas the weakest correlation was for the sugars. CONCLUSION: The tool proposed in this study could be applied to identify the country origin of the three types of multifloral honey considered here. It also offers promising perspectives for expanding knowledge of the provenance of honey. All of this could be achieved when a comprehensive database with the information generated by this electronic tongue has been created. © 2019 Society of Chemical IndustryThis study forms part of the projects funded by the Ministerio de Economía y Competitividad, the Agencia Estatal de Investigación, and the Fondo Europeo de Desarrollo Regional (AGL2016-77702-R) and by the Programa ADSIDEO-cooperación 2016 of the Centro de Cooperación al Desarrollo de la Universitat Politècnica de València, Spain, for which the authors are grateful.Sobrino-Gregorio, L.; Tanleque-Alberto, F.; Bataller Prats, R.; Soto Camino, J.; Escriche Roberto, MI. (2020). Using an automatic pulse voltammetric electronic tongue to verify the origin of honey from Spain, Honduras, and Mozambique. Journal of the Science of Food and Agriculture. 100(1):212-217. https://doi.org/10.1002/jsfa.10022S2122171001Kaškonienė, V., & Venskutonis, P. R. (2010). Floral Markers in Honey of Various Botanical and Geographic Origins: A Review. Comprehensive Reviews in Food Science and Food Safety, 9(6), 620-634. doi:10.1111/j.1541-4337.2010.00130.xSoares, S., Amaral, J. S., Oliveira, M. B. P. P., & Mafra, I. (2017). A Comprehensive Review on the Main Honey Authentication Issues: Production and Origin. Comprehensive Reviews in Food Science and Food Safety, 16(5), 1072-1100. doi:10.1111/1541-4337.12278El Alami El Hassani, N., Tahri, K., Llobet, E., Bouchikhi, B., Errachid, A., Zine, N., & El Bari, N. (2018). Emerging approach for analytical characterization and geographical classification of Moroccan and French honeys by means of a voltammetric electronic tongue. Food Chemistry, 243, 36-42. doi:10.1016/j.foodchem.2017.09.067Escriche, I., Tanleque-Alberto, F., Visquert, M., & Oroian, M. (2017). Physicochemical and rheological characterization of honey from Mozambique. LWT, 86, 108-115. doi:10.1016/j.lwt.2017.07.053Bougrini, M., Tahri, K., Saidi, T., El Alami El Hassani, N., Bouchikhi, B., & El Bari, N. (2016). Classification of Honey According to Geographical and Botanical Origins and Detection of Its Adulteration Using Voltammetric Electronic Tongue. Food Analytical Methods, 9(8), 2161-2173. doi:10.1007/s12161-015-0393-2Benedetti, S., Mannino, S., Sabatini, A. G., & Marcazzan, G. L. (2004). Electronic nose and neural network use for the classification of honey. Apidologie, 35(4), 397-402. doi:10.1051/apido:2004025Dias, L. A., Peres, A. M., Vilas-Boas, M., Rocha, M. A., Estevinho, L., & Machado, A. A. S. C. (2008). An electronic tongue for honey classification. Microchimica Acta, 163(1-2), 97-102. doi:10.1007/s00604-007-0923-8Wei, Z., Wang, J., & Liao, W. (2009). Technique potential for classification of honey by electronic tongue. Journal of Food Engineering, 94(3-4), 260-266. doi:10.1016/j.jfoodeng.2009.03.016Major, N., Marković, K., Krpan, M., Šarić, G., Hruškar, M., & Vahčić, N. (2011). Rapid honey characterization and botanical classification by an electronic tongue. Talanta, 85(1), 569-574. doi:10.1016/j.talanta.2011.04.025Wei, Z., & Wang, J. (2011). Classification of monofloral honeys by voltammetric electronic tongue with chemometrics method. Electrochimica Acta, 56(13), 4907-4915. doi:10.1016/j.electacta.2011.02.065Escriche, I., Kadar, M., Domenech, E., & Gil-Sánchez, L. (2012). A potentiometric electronic tongue for the discrimination of honey according to the botanical origin. Comparison with traditional methodologies: Physicochemical parameters and volatile profile. 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Antibody-Capped Mesoporous Nanoscopic Materials:Design of a Probe for the Selective Chromo-FluorogenicDetection of Finasteride

[EN] The synthesis of capped mesoporous silica nanoparticles (MSN) conjugated with an antibody (AB) as a gatekeeper has been carried out in order to obtain a delivery system able to release an entrapped cargo (dye) in the presence of a target molecule (antigen) to which the conjugated antibody binds selectively. In particular, MSN loaded with rhodamine B and functionalized on the external surface with a suitable derivative of N-(t-butyl)- 3-oxo-(5a,17b)-4-aza-androst-1-ene-17-carboxamide (finasteride) have been prepared (S1). The addition of polyclonal antibodies against finasteride induced capping of the pores due to the interaction with the anchored hapten-like finasteride derivative to give a MSN¿hapten¿AB nanoparticle S1-AB. It was found that the addition of capped material S1-AB to water solutions containing finasteride resulted in displacement of the antibody, pore uncapping and entrapped-dye release. The response of the gated material is highly selective, and only finasteride, among other steroids, was able to induce a significant uncapping process. Compared with finasteride, the finasteride metabolite was able to release 17% of the dye, whereas the exogen steroids testosterone, metenolone and 16-b-hydroxystanozolol only induced very little release of rhodamine B (lower than 10%) from aqueous suspensions containing sensing solid S1-AB. A detection limit as low as 20 ppb was found for the fluorimetric detection of finasteride. In order to evaluate a possible application of the material for label-free detection of finasteride, the capped material was isolated and stored to give final sensing solid S1-AB-i. It was found to display a similar behavior towards finasteride as to that shown by freshly prepared S1-AB; even after a period of two months, no significant loss of selectivity or sensitivity was noted. Moreover, to study the application for the detection of finasteride in biological samples, this ¿aged¿ material, S1-AB-i, was tested using commercially available blank urine as matrix. Samples containing 70 and 90% blank urine were spiked with a defined amount of finasteride, and the concentration was determined using capped S1-AB-i. Recovery ranges from 94% to 118% were reached.Financial support from the Spanish Government (project MAT2009-14564-C04-01) and the Generalitat Valenciana (Spain) (projects PROMETEO/2009/016 and PROMETEO/2010/008) is gratefully acknowledged. E. C. thanks the Minesterio de Ciencia e Innovacion (MICINN, Spain) for her fellowship.Climent Terol, E.; Martínez Mañez, R.; Maquieira Catala, Á.; Sancenón Galarza, F.; Marcos Martínez, MD.; Brun Sánchez, EM.; Soto Camino, J.... (2012). Antibody-Capped Mesoporous Nanoscopic Materials:Design of a Probe for the Selective Chromo-FluorogenicDetection of Finasteride. ChemistryOpen. 1:251-259. https://doi.org/10.1002/open.201100008S251259

Electro-responsive films containing voltage responsive gated mesoporous silica nanoparticles grafted onto PEDOT-based conducting polymer

[EN] The characteristics and electromechanical properties of conductive polymers together to their biocompatibility have boosted their application as a suitable tool in regenerative medicine and tissue engineering. However, conducting polymers as drug release materials are far from being ideal. A possibility to overcome this drawback is to combine conducting polymers with on-command delivery particles with inherent high-loading capacity. In this scenario, we report here the preparation of conduction polymers containing gated mesoporous silica nanoparticles (MSN) loaded with a cargo that is delivered on command by electro-chemical stimuli increasing the potential use of conducting polymers as controlled delivery systems. MSNs are loaded with Rhodamine B (Rh B), anchored to the conductive polymer poly(3,4-ethylenedioxythiophene) (PEDOT) doped with poly[(4-styrenesulfonic acid)-co-(maleic acid)], functionalized with a bipyridinium derivative and pores are capped with heparin (P3) by electrostatic interactions. P3 releases the entrapped cargo after the application of ¿640 mV voltage versus the saturated calomel electrode (SCE). Pore opening in the nanoparticles and dye delivery is ascribed to both (i) the reduction of the grafted bipyridinium derivative and (ii) the polarization of the conducting polymer electrode to negative potentials that induce detachment of positively charged heparin from the surface of the nanoparticles. Biocompatibility and cargo release studies were carried out in HeLa cells cultures.Alba Garcia-Fernandez, Beatriz Lozano-Torres contributed equally to this work. A. Garcia-Fernandez and B. Lozano-Torres are grateful to the "Ministerio de Economia y Competitividad" of the Spanish Government for her PhD fellowships. J. F. Blandez thanks the "Universitat Politecnica de Valencia" for his postdoctoral fellowship (PAID-10-17). The authors thank to the Spanish Government (Projects RTI2018-100910-B-C41 and RTI2018-101599-B-C22 (MCUI/AEI/FEDER, EU)) and the Generalitat Valencia (Project PROMETEO2018-024) for support.García-Fernández, A.; Lozano-Torres, B.; Blandez, JF.; Monreal-Trigo, J.; Soto Camino, J.; Collazos-Castro, JE.; Alcañiz Fillol, M.... (2020). Electro-responsive films containing voltage responsive gated mesoporous silica nanoparticles grafted onto PEDOT-based conducting polymer. Journal of Controlled Release. 323:421-430. https://doi.org/10.1016/j.jconrel.2020.04.048S421430323Aznar, E., Oroval, M., Pascual, L., Murguía, J. R., Martínez-Máñez, R., & Sancenón, F. (2016). Gated Materials for On-Command Release of Guest Molecules. 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