Virtual Issue: Molecular Sensors

Martínez-Máñez, R. (2014). Virtual Issue: Molecular Sensors. ChemistryOpen. 3(6):232-232. doi:10.1002/open.201402070S2322323

Zeolites synthesis using as a raw material the aluminium anodizing sludges

[EN] There were found, by atomic absorption and scanning electronic microscopy techniques, concentrations in between of 25,3% and 39,45% of aluminium respectively, in the anodized aluminium sludge on an industry that operates in Ecuador. Besides there were identified minor concentrations of Na, Mg, Ca and Si. Therefore the objective of the present research was to investigate, at the laboratory level, the feasibility of using these industrial residues as a source of precursors for the zeolites synthesis. The chemical composition of a fixed 20 g of sludge was adjusted by using a sodium hydroxide solutions in a varying concentrations of 0,5 M, 1,0 M, 1,5 M, 2,0 M, 2,5 M and 3,0 M in a mixture with hydrated Na2SiO3 in a constant amount added to the raw material. Molar ratio SiO2/Al2O was kept constant at 1,24 value, whereas the Na2O/Al2O3; Na2O/SiO2 and H2O/Na2O were varied as sodium hydroxide solutions changed in concentration. The processes of precursor's dilution, aging and zeolite crystallization were carried out a constant temperature of 100 degrees C for a 48 hours reaction time. By the X-ray diffraction technique, the synthesis of the Na-P1 GIS zeolite [Na-6(H2O)(12)][Si10Al6O32] was identified, with three types of mineralogy. Besides the zeolites ACP-1 and Sodalite Octahydrate were identified. The electronic images show a product with a well-defined morphology. The optimum conditions for the synthesis were the 1.5 M concentration of the caustic soda solution, and molar ratios of 1,24 SiO2/Al2O3; 0,61 Na2O/Al2O3; 2,02 SiO2/Na2O; 15,51 H2O/Na2O and 7,68 H2O/SiO2. At higher concentrations of the sodium hydroxide solution, the same zeolites were obtained, as evidenced by X-ray diffractograms, but the electronic images of the products show deformed crystals, possibly due to the excess of sodium hydroxide.[ES] Se encontró, por absorción atómica y escaneado electrónico de barrido concentraciones entre 25,3% y 39,45 % de aluminio, además de sodio, magnesio, calcio y silicio en los lodos de anodizado de aluminio de una industria que opera en Ecuador. Por lo tanto el objetivo del presente trabajo fue investigar a nivel de laboratorio, la posibilidad de utilizar estos residuos como fuente de precursores en la síntesis de zeolitas. Utilizando una solución de hidróxido de sodio en concentraciones 0,5M, 1,0 M, 1,5 M, 2,0 M, 2,5 M y 3,0 M en mezcla con Na2SiO3 hidratado, se ajustó la composición química de 20 g de muestra de lodo a una constante de relación molar SiO2/Al2O3 de 1,24 para todas las pruebas y variando las relaciones molares de Na2O/Al2O3; Na2O/SiO2 y H2O/ Na2O, conforme a la variación de la concentración de la solución de hidróxido de sodio. Se mantuvo constante la temperatura de fusión de precursores, envejecimiento y cristalización de la zeolita a 100°C y tiempo de reacción de 48 horas. Mediante la técnica de difracción de rayos X, se identificó la síntesis de la zeolita Na-P1 GIS , con tres tipos de mineralogía, además las zeolitas ACP-1 y Sodalita Octahidrato. Las imágenes electrónicas muestran un producto con una morfología bien definida. Las mejores condiciones del resultado fueron la concentración 1,5 M de la solución de sosa y relaciones molares 1,24 de SiO2/Al2O3; 0,61 de Na2O/Al2O3; 2,02 de SiO2/Na2O; 15,51, de H2O/ Na2O y 7,68 de H2O/ SiO2. A mayores concentraciones de sosa se obtienen las mismas zeolitas, como lo demuestran los difractogramas de rayos X, pero las imágenes electrónicas de los productos muestran cristales deformados, posiblemente por el exceso de sosa.Peñafiel-Villarreal, F.; Martínez-Máñez, R. (2019). Sintesis de Zeolitas utilizando como materia prima lodos de los procesos de anodizado de aluminio. Tecnología en Marcha. 32(3):12-23. https://doi.org/10.18845/tm.v32i3.4476S122332

Microalgae degradation follow up by voltammetric electronic tongue, impedance spectroscopy and NMR spectroscopy

[EN] Microalgae play a fundamental role in aquatic primary production and the food chain. They are a recognized source of fatty acids and fatty acid-based lipids of potential interest in the preparation of functional health products, biofuels and renewable chemicals. The exploitation of this bioresource requires a fine monitoring of each production stage. The aim of this work is the microalgae degradation follow up after the concentration stage at the end of the production process by voltammetric electronic tongue, impedance spectroscopy and H-1 NMR spectroscopy. Microalgae samples were allowed to progress along time (from 1 to 23 days). At scheduled selected times, voltammetry, impedance spectroscopy and H-1 NMR measurements were performed. Multivariate analysis was carried out on these data by PLSR. A model calculated in a training set was then applied to a set of validation to predict the time of evolution. For the three techniques good results in prediction for the validation set were obtained (R-2/RMSEP of 0.961/1.51, 0.956/1.67 and 0.969/1.25 respectively for impedance, voltammetry and NMR spectroscopy). The three techniques were sensitive to the evolution of the microalgae samples. The detection of metabolical changes in the H-1 NMR spectra is also included. This proof of concept could be the basis for future development of rapid and robust strategies for quality control on microalgae production plants.Authors gratefully acknowledge the financial support of MAT2015-64139-C4-1-R and MAT2015-64139-C4-3-R (MINECO/FEDER, UE) and PROMETEOII/2014/047 projects. BUGGYPOWER, S.L. is acknowledged for the financial support and for providing the samples. U26 Nanbiosis is acknowledged by the NMR measurements.Martínez-Bisbal, M.; Carbó-Mestre, N.; Martínez-Máñez, R.; Bauzá, J.; Alcañiz Fillol, M. (2019). Microalgae degradation follow up by voltammetric electronic tongue, impedance spectroscopy and NMR spectroscopy. Sensors and Actuators B Chemical. 281:44-52. https://doi.org/10.1016/j.snb.2018.10.069S445228

A Versatile New Paradigm for the Design of Optical Nanosensors Based on Enzyme-Mediated Detachment of Labeled Reporters: The Example of Urea Detection

"This is the peer reviewed version of the following article: Llopis-Lorente, Antoni, Reynaldo Villalonga, M. Dolores Marcos, Ramón Martínez-Máñez, and Félix Sancenón. 2018. A Versatile New Paradigm for the Design of Optical Nanosensors Based on Enzyme‐Mediated Detachment of Labeled Reporters: The Example of Urea Detection. Chemistry A European Journal 25 (14). Wiley: 3575 81. doi:10.1002/chem.201804706. , which has been published in final form at https://doi.org/10.1002/chem.201804706. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving."[EN] Here, a new bio-inspired nanoarchitectonics approach for the design of optical probes is presented. It is based on nanodevices that combine 1) an enzymatic receptor subunit, 2) a signaling subunit (consisting of a labeled reporter attached to a silica surface), and 3) a mechanism of communication between the two sites based on the production of chemical messengers by the enzymatic subunit, which induces the detachment of the reporter molecules from the silica surface. As a proof of concept, a urea nanosensor based on the release of Alexa-Fluor-647-labeled oligonucleotide from enzyme-functionalized Janus gold-mesoporous-silica nanoparticles (Au-MSNPs) was developed. The Janus particles were functionalized on the silica face with amino groups to which the labeled oligonucleotides were attached by electrostatic interactions, whereas the gold face was used for grafting urease enzymes. The nanodevice was able to release the fluorescent oligonucleotide through the enzyme-mediated hydrolysis of urea to ammonia and the subsequent deprotonation of amino groups on the silica face. This simple nanodevice was applied for the fluorometric detection of urea in real human blood samples and for the identification of adulterated milk. Given the large variety of enzymes and reporter species that could be combined, this is a general new paradigm that could be applied to the design of a number of optical probes for the detection of target analytes.A.L.-L. is grateful to "La Caixa" Banking Foundation for his Ph.D. fellowship. The authors thank to the Spanish Government (MINECO Projects MAT2015-64139-C4-1, AGL2015-70235-C2-2-R, CTQ2014-58989-P and CTQ2015-71936-REDT) and the Generalitat Valencia (Projects PROMETEOII/2014/047, PROMETEO2018/024) for support. The Comunidad de Madrid (S2013/MIT-3029, Programme NANOAVANSENS) is also gratefully acknowledged.Llopis-Lorente, A.; Villalonga, R.; Marcos Martínez, MD.; Martínez-Máñez, R.; Sancenón Galarza, F. (2019). A Versatile New Paradigm for the Design of Optical Nanosensors Based on Enzyme-Mediated Detachment of Labeled Reporters: The Example of Urea Detection. Chemistry - A European Journal. 25(14):3575-3581. https://doi.org/10.1002/chem.201804706S35753581251

Fluorogenic Detection of Human Serum Albumin Using Curcumin-Capped Mesoporous Silica Nanoparticles

[EN] Mesoporous silica nanoparticles loaded with rhodamine B and capped with curcumin are used for the selective and sensitive fluorogenic detection of human serum albumin (HSA). The sensing mesoporous silica nanoparticles are loaded with rhodamine B, decorated with aminopropyl moieties and capped with curcumin. The nanoparticles selectively release the rhodamine B cargo in the presence of HSA. A limit of detection for HSA of 0.1 mg/mL in PBS (pH 7.4)-acetonitrile 95:5 v/v was found, and the sensing nanoparticles were used to detect HSA in spiked synthetic urine samples.This research was funded by the Spanish Government (RTI2018-100910-B-C41 (MCUI/FEDER, EU)) and the Generalitat Valenciana (PROMETEO 2018/024). I.O. was funded by Erasmus Mundus Programme, Action 2, Lot 1, Syria (predoctoral fellowship). S.M. was funded by Generalitat Valenciana (Santiago Grisolia fellowship).Otri, I.; Medaglia, S.; Aznar, E.; Sancenón Galarza, F.; Martínez-Máñez, R. (2022). Fluorogenic Detection of Human Serum Albumin Using Curcumin-Capped Mesoporous Silica Nanoparticles. Molecules. 27(3):1-9. https://doi.org/10.3390/molecules270311331927

Sucrose-responsive intercommunicated janus nanoparticles network

[EN] Inspired by biological systems, the development of artificial nanoscale materials that communicate over a short distance is still at its early stages. This work shows a new example of a cooperating system with intercommunicated devices at the nanoscale. The system is based on the new sucrose-responsive Janus gold-mesoporous silica (Janus Au-MS) nanoparticles network with two enzyme-powered nanodevices. These nanodevices involve two enzymatic processes based on invertase and glucose oxidase, which are anchored on the Au surfaces of different Janus Au-MS nanoparticles, and N-acetyl-L-cysteine and [Ru(bpy)(3)](2+) loaded as chemical messengers, respectively. Sucrose acts as the INPUT, triggering the sequential delivery of two different cargoes through the enzymatic control. Nanoscale communication using abiotic nanodevices is a developing potential research field and may prompt several applications in different disciplines, such as nanomedicine.Financial support was provided by the Spanish Ministry of Economy and Competitiveness (MINECO Projects CTQ2017-87954-P). D.V. thanks MICINN for the Juan de la Cierva fellowship (IJC2018-035658-I). R.M.-M. thanks the Generalitat Valenciana (Project PROMETEO2018/024).Jiménez-Falcao, S.; Torres, D.; Martínez-Ruiz, P.; Vilela, D.; Martínez-Máñez, R.; Villalonga, R. (2021). Sucrose-responsive intercommunicated janus nanoparticles network. Nanomaterials. 11(10):1-11. https://doi.org/10.3390/nano11102492111111

Chromo-fluorogenic probes for beta-galactosidase detection

[EN] beta-Galactosidase (beta-Gal) is a widely used enzyme as a reporter gene in the field of molecular biology which hydrolyzes the beta-galactosides into monosaccharides. beta-Gal is an essential enzyme in humans and its deficiency or its overexpression results in several rare diseases. Cellular senescence is probably one of the most relevant physiological disorders that involve beta-Gal enzyme. In this review, we assess the progress made to date in the design of molecular-based probes for the detection of beta-Gal both in vitro and in vivo. Most of the reported molecular probes for the detection of beta-Gal consist of a galactopyranoside residue attached to a signalling unit through glycosidic bonds. The beta-Gal-induced hydrolysis of the glycosidic bonds released the signalling unit with remarkable changes in color and/or emission. Additional examples based on other approaches are also described. The wide applicability of these probes for the rapid and in situ detection of de-regulation beta-Gal-related diseases has boosted the research in this fertile fieldR.M laboratory members received the financial support from the Spanish Government (project RTI2018-100910-B-C41) and the Generalitat Valenciana (project PROMETEO 2018/024). B.L-T. received support from the Spanish Ministry of Economy for their PhD grants (FPU15/02707). J. F.-B received fellowship (CD19/00038)Lozano-Torres, B.; Blandez, JF.; Sancenón Galarza, F.; Martínez-Máñez, R. (2021). Chromo-fluorogenic probes for beta-galactosidase detection. Analytical and Bioanalytical Chemistry. 413(9):2361-2388. https://doi.org/10.1007/s00216-020-03111-8S236123884139Fernandes P. Enzymes in food processing: a condensed overview on strategies for better biocatalysts. Enzyme Res. 2010;2010:86253–73.Likidlilid A, Patchanans N, Peerapatdit T, Sriratanasathavorn C. 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Development of a textile nanocomposite as naked eye indicator of the exposition to strong acids

[EN] Chemical burns, mainly produced by acids, are a topic of concern. A new sensing material for the detection of strong acids able to be incorporated into textiles has been developed. The material is prepared by the covalent attachment of 2,2 ',4,4 ',4 ''-pentamethoxy triphenyl methanol to a mesoporous material which further is included in a nitro resin to obtain a colourless composite. The response of this composite to diverse acid solutions was tested showing the appearance of an intense purple colour (with a colour difference higher than 160) that can be monitored by the naked eye or could be easily digitised to feed an instrumental sensor. Reversibility and resistance to washing cycles were studied with positive results. Finally, the response of the sensing composite to acid vapours was assayed, observing a colour change similar to that found in solution.The authors thank the financial support from the Spanish Government (project MAT2015-64139-C4-1-R) and the Generalitat Valenciana (project PROMETEOII/2014/047).Pallas, I.; Marcos Martínez, MD.; Martínez-Máñez, R.; Ros-Lis, JV. (2017). Development of a textile nanocomposite as naked eye indicator of the exposition to strong acids. Sensors. 17(9):1-12. https://doi.org/10.3390/s17092134S112179MCCOY, M. (2008). MADE IN WISCONSIN. Chemical & Engineering News, 86(19), 27. doi:10.1021/cen-v086n019.p027Koh, D.-H., Lee, S.-G., & Kim, H.-C. (2017). Incidence and characteristics of chemical burns. Burns, 43(3), 654-664. doi:10.1016/j.burns.2016.08.037Ye, C., Wang, X., Zhang, Y., Ni, L., Jiang, R., Liu, L., & Han, C. (2016). Ten-year epidemiology of chemical burns in western Zhejiang Province, China. Burns, 42(3), 668-674. doi:10.1016/j.burns.2015.12.004Ghahremani Honarvar, M., & Latifi, M. (2016). Overview of wearable electronics and smart textiles. The Journal of The Textile Institute, 108(4), 631-652. doi:10.1080/00405000.2016.1177870Stoppa, M., & Chiolerio, A. (2014). Wearable Electronics and Smart Textiles: A Critical Review. Sensors, 14(7), 11957-11992. doi:10.3390/s140711957Van der Schueren, L., & De Clerck, K. (2012). Coloration and application of pH-sensitive dyes on textile materials. Coloration Technology, 128(2), 82-90. doi:10.1111/j.1478-4408.2011.00361.xStaneva, D., Betcheva, R., & Chovelon, J.-M. (2007). Optical sensor for aliphatic amines based on the simultaneous colorimetric and fluorescence responses of smart textile. Journal of Applied Polymer Science, 106(3), 1950-1956. doi:10.1002/app.26724Steyaert, I., Vancoillie, G., Hoogenboom, R., & De Clerck, K. (2015). Dye immobilization in halochromic nanofibers through blend electrospinning of a dye-containing copolymer and polyamide-6. Polymer Chemistry, 6(14), 2685-2694. doi:10.1039/c5py00060bDe Meyer, T., Steyaert, I., Hemelsoet, K., Hoogenboom, R., Van Speybroeck, V., & De Clerck, K. (2016). Halochromic properties of sulfonphthaleine dyes in a textile environment: The influence of substituents. Dyes and Pigments, 124, 249-257. doi:10.1016/j.dyepig.2015.09.007Martínez-Máñez, R., & Sancenón, F. (2003). Fluorogenic and Chromogenic Chemosensors and Reagents for Anions. Chemical Reviews, 103(11), 4419-4476. doi:10.1021/cr010421eQuang, D. T., & Kim, J. S. (2010). Fluoro- and Chromogenic Chemodosimeters for Heavy Metal Ion Detection in Solution and Biospecimens. Chemical Reviews, 110(10), 6280-6301. doi:10.1021/cr100154pZhang, X., Yin, J., & Yoon, J. (2014). Recent Advances in Development of Chiral Fluorescent and Colorimetric Sensors. Chemical Reviews, 114(9), 4918-4959. doi:10.1021/cr400568bSalinas, Y., Ros-Lis, J. V., Vivancos, J.-L., Martínez-Máñez, R., Marcos, M. D., Aucejo, S., … Lorente, I. (2012). Monitoring of chicken meat freshness by means of a colorimetric sensor array. The Analyst, 137(16), 3635. doi:10.1039/c2an35211gEsteban, J., Ros-Lis, J. V., Martínez-Máñez, R., Marcos, M. D., Moragues, M., Soto, J., & Sancenón, F. (2010). Sensitive and Selective Chromogenic Sensing of Carbon Monoxide by Using Binuclear Rhodium Complexes. Angewandte Chemie International Edition, 49(29), 4934-4937. doi:10.1002/anie.201001344Scott, B. J., Wirnsberger, G., & Stucky, G. D. (2001). Mesoporous and Mesostructured Materials for Optical Applications. Chemistry of Materials, 13(10), 3140-3150. doi:10.1021/cm0110730Melde, B., Johnson, B., & Charles, P. (2008). Mesoporous Silicate Materials in Sensing. Sensors, 8(8), 5202-5228. doi:10.3390/s8085202Wagner, T., Haffer, S., Weinberger, C., Klaus, D., & Tiemann, M. (2013). Mesoporous materials as gas sensors. Chem. Soc. Rev., 42(9), 4036-4053. doi:10.1039/c2cs35379bAznar, E., Mondragón, L., Ros-Lis, J. V., Sancenón, F., Marcos, M. D., Martínez-Máñez, R., … Amorós, P. (2011). Finely Tuned Temperature-Controlled Cargo Release Using Paraffin-Capped Mesoporous Silica Nanoparticles. Angewandte Chemie International Edition, 50(47), 11172-11175. doi:10.1002/anie.201102756Coll, C., Ros-Lis, J. V., Martínez-Máñez, R., Marcos, M. D., Sancenón, F., & Soto, J. (2010). A new approach for the selective and sensitive colorimetric detection of ionic surfactants in water. J. Mater. Chem., 20(8), 1442-1451. doi:10.1039/b910659fRos-Lis, J. V., Casasús, R., Comes, M., Coll, C., Marcos, M. D., Martínez-Máñez, R., … Rurack, K. (2008). A Mesoporous 3D Hybrid Material with Dual Functionality for Hg2+Detection and Adsorption. Chemistry - A European Journal, 14(27), 8267-8278. doi:10.1002/chem.200800632Sanfeliu, C., Martínez-Máñez, R., Sancenón, F., Soto, J., Puchol, V., Amorós, P., & Marcos, M. D. (2012). Low-cost materials for boron adsorption from water. Journal of Materials Chemistry, 22(48), 25362. doi:10.1039/c2jm32819dDescalzo, A. B., Martínez-Máñez, R., Sancenón, F., Hoffmann, K., & Rurack, K. (2006). The Supramolecular Chemistry of Organic–Inorganic Hybrid Materials. Angewandte Chemie International Edition, 45(36), 5924-5948. doi:10.1002/anie.200600734Descalzo, A. B., Jimenez, D., Marcos, M. D., Martínez-Máñez, R., Soto, J., El Haskouri, J., … Borrachero, M. V. (2002). A New Approach to Chemosensors for Anions Using MCM-41 Grafted with Amino Groups. Advanced Materials, 14(13-14), 966-969. doi:10.1002/1521-4095(20020705)14:13/143.0.co;2-

Nanotechnology in the Development of Novel Functional Foods or their Package. An Overview Based in Patent Analysis

[EN] In recent years nanotechnology has become a significant component in food industry. It is present in all food chain steps, from the design of new ingredients or additives, to the most modern systems of food quality methods or packaging, demonstrating the great potential of this new technology in a sector as traditional as food. However, while interest by industry in nanotechnology increases, the rejection by consumers, concerned about the potential risk, does too. The aim of this review is to evaluate the development of food nanotechnology by means of a patent analysis, highlighting current applications of nanotechnology along the whole food chain and contextualizing this evolution in the social scene.Financial support from the Spanish Government (project MAT2009-14564-C04-01 and AGL2010-20539) and the Generalitat Valencia (project PROMETEO/2009/016) are gratefully acknowledged. E.P. thanks the Ministerio de Educación for a fellowshipPérez-Esteve, É.; Bernardos Bau, A.; Martínez-Máñez, R.; Barat Baviera, JM. (2013). Nanotechnology in the Development of Novel Functional Foods or their Package. An Overview Based in Patent Analysis. Recent Patents on Food, Nutrition and Agriculture. 5(1):35-43. https://doi.org/10.2174/2212798411305010006S35435

Recent advances on intelligent packaging as tools to reduce food waste

[EN] Food waste is one of the main issues for international organisms. It is not only an ethical and economic issue but it also depletes the environment of limited natural resources. Among strategies suitable for fighting such challenge, intelligent packaging is an interesting tool to reduce waste derived from households and retailers. A revision of 45 recent advances in the area of optical systems for freshness monitoring is reported herein. The study covers fruits, vegetables, fish products and meat since they are the most representative fields of application. Furthermore, a discussion about the main research challenges and opportunities that will be faced by intelligent packaging in the coming years is included. (C) 2017 Elsevier Ltd. All rights reserved.The authors thank financial support from the Spanish Government (project MAT2015-64139-C4-1-R) and the Generalitat Valenciana (project (Project PROMETEOII/2014/047).Poyatos-Racionero, E.; Ros-Lis, JV.; Vivancos, J.; Martínez-Máñez, R. (2018). Recent advances on intelligent packaging as tools to reduce food waste. Journal of Cleaner Production. 172:3398-3409. https://doi.org/10.1016/j.jclepro.2017.11.075S3398340917