Progress on the preparation of nanocrystalline apatites and surface characterization: Overview of fundamental and applied aspects

Nanocrystalline calcium phosphate apatites constitute the main inorganic part of hard tissues, and a growing focus is devoted to prepare synthetic analogs, so-called “biomimetic”, able to precisely mimic the morphological and physico-chemical features of biological apatite compounds. Both from fundamental and applied viewpoints, an accurate characterization of nanocrystalline apatites, including their peculiar surface features, and a deep knowledge of crystallization aspects are prerequisites to attempt understanding mineralization phenomena in vivo as well as for designing innovative bioactive materials that may then find applications in bone tissue engineering, either as self-supported scaffolds and fillers or in the form of coatings, but also in other domains such as drug delivery or else medical imaging. Also,interfacial phenomena are of prime importance for getting a better insight of biomineralization and for following the behavior of biomaterials in or close to their final conditions of use. In this view,both adsorption and ion exchange represent essential processes involving the surface of apatite nanocrystals, possibly doped with foreign elements or functionalized with organic molecules of interest. In this review paper, we will address these various points in details based on a large literature survey. We will also underline the fundamental physico-chemical and behavioral differences that exist between nanocrystalline apatites (whether of biological origin or their synthetic biomimetic analogs) and stoichiometric hydroxyapatite

Biomimetic Mineralization Promotes Viability and Differentiation of Human Mesenchymal Stem Cells in a Perfusion Bioreactor

In bone tissue engineering, the design of 3D systems capable of recreating composition, architecture and micromechanical environment of the native extracellular matrix (ECM) is still a challenge. While perfusion bioreactors have been proposed as potential tool to apply biomechanical stimuli, its use has been limited to a low number of biomaterials. In this work, we propose the culture of human mesenchymal stem cells (hMSC) in biomimetic mineralized recombinant collagen scaffolds with a perfusion bioreactor to simultaneously provide biochemical and biophysical cues guiding stem cell fate. The scaffolds were fabricated by mineralization of recombinant collagen in the presence of magnesium (RCP.MgAp). The organic matrix was homogeneously mineralized with apatite nanocrystals, similar in composition to those found in bone. X-Ray microtomography images revealed isotropic porous structure with optimum porosity for cell ingrowth. In fact, an optimal cell repopulation through the entire scaffolds was obtained after 1 day of dynamic seeding in the bioreactor. Remarkably, RCP.MgAp scaffolds exhibited higher cell viability and a clear trend of up-regulation of osteogenic genes than control (non-mineralized) scaffolds. Results demonstrate the potential of the combination of biomimetic mineralization of recombinant collagen in presence of magnesium and dynamic culture of hMSC as a promising strategy to closely mimic bone ECM.EU Marie Curie Project "Bio-Inspired Bone Regeneration" 607051Spanish Ministry of Science, Innovation and Universities (MCIU) RYC-2016-21042 RTI-2018-095794A-C22Interdisciplinary Center for Clinical Research (IZKF) at the University ofWuerzburg D-361MCI

Two-Sided Antibacterial Cellulose Combining Probiotics and Silver Nanoparticles

This work was funded by the Spanish Ministerio de Ciencia, Innovacion y Universidades (MICIU) (projects FEDER PID2019-111461GB-I00 and Ramon y Cajal RYC-2016-21042). L.S. acknowledges the Spanish MICIU for the predoctoral contract within the FPU program (FPU16/01360).The constant increase of antibiotic-resistant bacteria demands the design of novel antibiotic-free materials. The combination of antibacterials in a biocompatible biomaterial is a very promising strategy to treat infections caused by a broader spectrum of resistant pathogens. Here, we combined two antibacterials, silver nanoparticles (AgNPs) and living probiotics (Lactobacillus fermentum, Lf), using bacterial cellulose (BC) as scaffold. By controlling the loading of each antibacterial at opposite BC sides, we obtained a two-sided biomaterial (AgNP-BC-Lf) with a high density of alive and metabolically active probiotics on one surface and AgNPs on the opposite one, being probiotics well preserved from the killer effect of AgNPs. The resulting two-sided biomaterial was characterized by Field-Emission Scanning Electron Microscopy (FESEM) and Confocal Laser Scanning Microscopy (CLSM). The antibacterial capacity against Pseudomonas aeruginosa (PA), an opportunistic pathogen responsible for a broad range of skin infections, was also assessed by agar diffusion tests in pathogen-favorable media. Results showed an enhanced activity against PA when both antibacterials were combined into BC (AgNP-BC-Lf) with respect to BC containing only one of the antibacterials, BC-Lf or AgNP-BC. Therefore, AgNP-BC-Lf is an antibiotic-free biomaterial that can be useful for the therapy of topical bacterial infections.Spanish Ministerio de Ciencia, Innovacion y Universidades (MICIU) (project FEDER) PID2019-111461GB-I00Spanish Ministerio de Ciencia, Innovacion y Universidades (MICIU) (Project Ramon y Cajal) RYC-2016-21042Spanish MICIU FPU16/0136

Effects of Methyl Jasmonate and Nano-Methyl Jasmonate Treatments on Monastrell Wine Volatile Composition

This work has been supported by funding provided by the Spanish MCIN/AEI/10.13039/501100011033 and "ERDF, A way of making Europe" through the projects NanoVIT (RTI-2018-095794-B-C21 and RTI-2018-095794-A-C22), and by the Junta de Andalucia with the project NanoFERTi (P18-TP-969). GBRR also acknowledges Junta de Andalucia for her postdoctoral contract within the PAIDI 2020 program (DOC_01383).The application of methyl jasmonate (MeJ) as an elicitor to enhance secondary metabolites in grapes and wines has been studied, but there is little information about its use in conjunction with nanotechnology and no information about its effects on wine volatile compounds. This led us to study the impact of nanoparticles doped with MeJ (Nano-MeJ, 1mM MeJ) on the volatile composition of Monastrell wines over three seasons, compared with the application of MeJ in a conventional way (10 mM MeJ). The results showed how both treatments enhanced fruity esters in wines regardless of the vintage year, although the increase was more evident when grapes were less ripe. These treatments also achieved these results in 2019 in the cases of 1-propanol, ß-phenyl-ethanol, and methionol, in 2020 in the cases of hexanol and methionol, and in 2021, but only in the case of hexanol. On the other hand, MeJ treatment also increased the terpene fraction, whereas Nano-MeJ, at the applied concentration, did not increase it in any of the seasons. In summary, although not all families of volatile compounds were increased by Nano-MeJ, the Nano-MeJ treatment generally increased the volatile composition to an extent similar to that obtained with MeJ used in a conventional way, but at a 10 times lower dose. Therefore, the use of nanotechnology could be a good option for improving the quality of wines from an aromatic point of view, while reducing the necessary dosage of agrochemicals, in line with more sustainable agricultural practices.Junta de Andalucia P18-TP-969 DOC_01383Spanish MCIN/AEI"ERDF, A way of making Europe" through the projects NanoVIT RTI-2018-095794-B-C21 RTI-2018-095794-A-C2

On the amorphous layer in bone mineral and biomimetic apatite: A combined small- and wide-angle X-ray scattering analysis

The occurrence of an amorphous calcium phosphate layer covering the crystalline apatite core has been suggested to be an intrinsic feature of both bone mineral and synthetic biomimetic analogs. However, an exahustive quantitative picture of the amorphous-crystalline relationship in these materials is still miss- ing. Here, we present a multiple scale modelling that combines small-angle X-ray scattering (SAXS) and synchrotron wide-angle X-ray total scattering (WAXTS) analyses to investigate the amorphous-crystalline spatial interplay in bone sample and biomimetic carbonated nano-apatites. SAXS analysis indicates the presence of a single morphology consisting of tiny nanoplates (NPLs) and provides a measure of their thickness (falling in the 3–5 nm range). WAXTS analysis was performed by developing atomistic models of apatite NPLs incorporating lattice strain, mostly attributed to the carbonate content, and calculating the X-ray patterns using the Debye Scattering Equation. Upon model optimization, the size and strain parameters of the crystalline platelets were derived and the amorphous component, co-existing with the crystalline one, separated and quantified (in the 23–33 wt% range). Notably, the thickness of the ap- atite core was found to exhibit nearly null (bone) or minor ( < 0.5 nm, biomimetic samples) deviations from that of the entire NPLs, suggesting that the amorphous material remains predominantly distributed along the lateral sides of the NPLs, in a core-crown-like arrangement. The lattice strain analysis indicates a significant stiffness along the c axis, which is comparable in bone and synthetic samples, and larger deformations in the other directions. Statement of Significance Current models of bone mineral and biomimetic nanoapatites suggest the occurrence of an amorphous layer covering the apatitic crystalline nanoplates in a core-shell arrangement. By combining X-ray scatter- ing techniques in the small and wide angle regions, we propose a joint atomic-to-nanometre scale mod- elling to investigate the amorphous-crystalline interplay within the nanoplates. Estimates are extracted for the thickness of the entire nanoplates and the crystalline core, together with the quantification of the amorphous fraction and apatite lattice strain. Based on the thickness matching, the location of the amorphous material mostly along the edges of the nanoplates is inferred, with a vanishing or very thin layer in the thickness direction, suggesting a core-crown-like arrangement, with possible implications on the mineral surface reactivity.Fondazione Cariplo 2016-0648FEDER/Ministerio de Ciencia, Innovación y Universidades-Agencia Estatal de Investigación (FEDER/MCIU/AEI) RYC-2016-21042 RTI-2018-095794-A-C22FEDER/MCIU/AEI JdC-201

Effects of school-based physical activity and nutrition programs in spanish adolescents: systematic review

Introducción: la inactividad física y las conductas de alimentación poco saludable desde edades tempranas son dos de los grandes problemas de salud pública en los países desarrollados. Objetivo: realizar una revisión sistemática de los programas de promoción de actividad física y/o de alimentación desarrollados en España con adolescentes, desde el ámbito educativo y publicados en las principales bases de datos nacionales e internacionales en los últimos quince años. Método: se han revisado los artículos originales en inglés y español publicados en las bases de datos electrónicas: Web of Science, Scopus, ERIC, PsycINFO, Dialnet e ISOC, teniendo en cuenta los principios establecidos por la declaración PRISMA para revisiones sistemáticas. Resultados y discusión: de los 522 artículos identificados, 13 cumplían los criterios de inclusión establecidos. El aspecto de mayor coincidencia en los trabajos analizados es el de involucrar a las familias en la intervención. Al mismo tiempo, destaca el protagonismo del profesorado de Educación Física en la implementación de los programas, junto a la figura de los sanitarios, que también adquieren un elevado protagonismo. En todos ellos se logró incidir positivamente, como mínimo, en una de las variables objeto de estudio. Conclusión: en los últimos 15 años solamente se han identificado 13 programas con adolescentes de promoción de actividad física y/o de alimentación en España. Pero en todos ellos se obtuvieron mejoras, lo que confirma el relevante papel de la institución educativa sobre la adquisición y/o mejora de dichos hábitos desde una perspectiva saludable.Background: physical inactivity and unhealthy nutrition behaviours in early ages are two of the biggest problems related with public health in developed countries. Aims: to carry out a systematic review of school-based programs related with physical activity promotion and/or nutrition in adolescents implemented in Spain and published in the principal national and international data bases in the last 15 years. Method: the literature was searched in spanish and english data bases Web of Science, ERIC, PsycINFO, Dialnet and ISOC, following PRISMA declaration principles for systematic reviews. Results and discussion: from a total of 522 references, were retained 13 studies due to inclusion criteria. The most prevalent programs included families participation in the intervention. At the same time, the Physical Education teachers and the health personnel were the principal actor in programs development. Both of them were the principal protagonist in interventions. All the programs were able to improve at least one of the variables. Conclusion: were identified only 13 school-based intervention programs related with physical activity and/or nutrition in adolescents in the last 15 years in Spain. All the programs reached improvements, so school shows a relevant role in acquisition or improvement of this health behavior

Bioinspired mineralization of engineered living materials to promote osteogenic differentiation

In this work, Engineered Living Materials (ELMs), based on the combination of genetically-modified bacteria and mineral-reinforced organic matrices, and endowed with self-healing or regenerative properties and adaptation to specific biological environments were developed. Concretely, we produced ELMs combining human mesenchymal stem cells (hMSCs) and Lactococcus lactis (L. lactis), which was specifically programmed to deliver bone morphogenetic protein (BMP-2) upon external stimulation using nisin, into mineralized alginate matrices. The hybrid organic/inorganic matrix was built through a protocol, inspired by bone mineralization, in which alginate (Alg) assembly and apatite (HA) mineralization occurred simultaneously driven by calcium ions. Chemical composition, structure and reologhical properties of the hybrid 3D matrices were dedicately optimized prior the incorportation of the living entities. Then, the same protocol was reproduced in the presence of hMSC and engineered L. lactis that secrete BMP-2 resulting in 3D hybrid living hydrogels. hMSC viability and osteogenic differentiation in the absence and presence of the bacteria were evaluated by live/dead and quantitative realtime polymerase chain reaction (qPCR) and immunofluorescence assays, respectively. Results demonstrate that these 3D engineered living material support osteogenic differentiation of hMSCs due to the synergistic effect between HA and the growth factors BMP-2 delivered by L. lactisEPSRC (EP/P001114/1)U.K. Regenerative Medicine Platform “Acellular/Smart Materials-3D Architecture” (MR/R015651/1)Junta de Andalucía through the collaborative project NanoFERTI (P18-TP-0969)The Spanish MCIN/AEI/10.13039/501100011033The “European Union” NextGenerationEU/PRTR (project number PDC2022-133191- I00)EMBO Scientific Exchange Grant (SEG number 9741)RYC2021-032734-IMCIN/AEI/10.13039/501100011033ESF Investing in your futur

A Gamification-Based Intervention Program that Encourages Physical Activity Improves Cardiorespiratory Fitness of College Students: ‘The Matrix rEFvolution Program’

J.M.-G. was supported by the Spanish Ministry of Education, Culture and Sport under Grant FPU14/06837. I.E.-C. was supported by the Spanish Ministry of Science and Innovation under Grant FJCI-2014-19563. Additional support was obtained from the University of Granada, Plan Propio de Investigación 2016, Excellence actions: Units of Excellence, Unit of Excellence on Exercise and Health (UCEES); and by the Junta de Andalucía, Consejería de Conocimiento, Investigación y Universidades and European Regional Development Fund (ERDF) (Ref. SOMM17/6107/UGR)The aim of the present study was to examine the effects of a gamification-based program on cardiorespiratory fitness (CRF) levels of college students. We divided 112 college students into an intervention group (IG) and a control group (CG). IG college students followed a 15-week gamification-based program, whereas CG followed traditional lectures. CRF was assessed using the 20-meter shuttle-run test. CRF significantly improved after the program in the IG compared to CG (d ≤ 0.94, p < 0.001). Only participants of IG had significant CRF improvements (d ≤ 0.87, p < 0.001) between pre- and post-assessments. In the IG, from the students who attended 100% of lectures, 87.8% met physical activity recommendations for 100% of weeks, whereas from those who attended <100%, only 26.7% met them them for 100% of weeks (p < 0.001). Participants who met recommendations 100% of weeks had a significant CRF improvement (p < 0.001). Motivating college students throughout innovative teaching methods (e.g., gamification) can lead to health improvements.European Regional Development Fund (ERDF) (Ref. SOMM17/6107/UGR

La Formación Dual Universitaria en el Grado en Ingeniería en Automoción de la IUE-EUI de Vitoria-Gasteiz. Requisitos de Calidad.

Congreso Universitario de Innovación Educativa En las Enseñanzas Técnicas, CUIEET (26º. 2018. Gijón

Upgrading of oxygenated compounds present in aqueous biomass-derived feedstocks over NbOx-based catalysts

[EN] The influence of synthesis and post-synthesis procedures of different niobium oxides on their catalytic performance in the aqueous phase condensation of oxygenated compounds is studied. Hydrothermally synthesized niobium oxide with a pseudo-crystalline structure shows enhanced acid properties, surface area and consequently better catalytic activity than Nb2O5 prepared by other synthesis methods. The optimized NbOx-based catalyst also demonstrates higher stability after several reuses compared to the Ce-Zr mixed oxide reference catalyst.Financial support by the Spanish Government (CTQ-2015-67592, CTQ-2015-68951-C3-1, and SEV-2012-0267) is gratefully acknowledged. A. F.-A. and D. D. thank the "La Caixa-Severo Ochoa" Foundation and the Severo Ochoa Excellence Program (SVP-2014-068669), respectively, for their fellowships. Authors also thank the Electron Microscopy Service of Universitat Politecnica de Valencia for their supportFernandez-Arroyo, A.; Delgado-Muñoz, D.; Domine, ME.; López Nieto, JM. (2017). Upgrading of oxygenated compounds present in aqueous biomass-derived feedstocks over NbOx-based catalysts. Catalysis Science & Technology. 7(23):5495-5499. https://doi.org/10.1039/c7cy00916jS54955499723Huber, G. W., Iborra, S., & Corma, A. (2006). Synthesis of Transportation Fuels from Biomass:  Chemistry, Catalysts, and Engineering. Chemical Reviews, 106(9), 4044-4098. doi:10.1021/cr068360dTuck, C. O., Perez, E., Horvath, I. T., Sheldon, R. A., & Poliakoff, M. (2012). Valorization of Biomass: Deriving More Value from Waste. Science, 337(6095), 695-699. doi:10.1126/science.1218930Huber, G. W., & Corma, A. (2007). Synergies between Bio- and Oil Refineries for the Production of Fuels from Biomass. Angewandte Chemie International Edition, 46(38), 7184-7201. doi:10.1002/anie.200604504Alonso, D. M., Bond, J. Q., & Dumesic, J. A. (2010). Catalytic conversion of biomass to biofuels. Green Chemistry, 12(9), 1493. doi:10.1039/c004654jPinheiro, A., Hudebine, D., Dupassieux, N., & Geantet, C. (2009). Impact of Oxygenated Compounds from Lignocellulosic Biomass Pyrolysis Oils on Gas Oil Hydrotreatment. Energy & Fuels, 23(2), 1007-1014. doi:10.1021/ef800507zBui, V. N., Toussaint, G., Laurenti, D., Mirodatos, C., & Geantet, C. (2009). Co-processing of pyrolisis bio oils and gas oil for new generation of bio-fuels: Hydrodeoxygenation of guaïacol and SRGO mixed feed. Catalysis Today, 143(1-2), 172-178. doi:10.1016/j.cattod.2008.11.024Asadieraghi, M., Wan Daud, W. M. A., & Abbas, H. F. (2014). Model compound approach to design process and select catalysts for in-situ bio-oil upgrading. Renewable and Sustainable Energy Reviews, 36, 286-303. doi:10.1016/j.rser.2014.04.050Cherubini, F., Jungmeier, G., Wellisch, M., Willke, T., Skiadas, I., Van Ree, R., & de Jong, E. (2009). Toward a common classification approach for biorefinery systems. Biofuels, Bioproducts and Biorefining, 3(5), 534-546. doi:10.1002/bbb.172Gaertner, C. A., Serrano-Ruiz, J. C., Braden, D. J., & Dumesic, J. A. (2009). Catalytic coupling of carboxylic acids by ketonization as a processing step in biomass conversion. Journal of Catalysis, 266(1), 71-78. doi:10.1016/j.jcat.2009.05.015Omata, K., Matsumoto, K., Murayama, T., & Ueda, W. (2016). Direct oxidative transformation of glycerol to acrylic acid over Nb-based complex metal oxide catalysts. Catalysis Today, 259, 205-212. doi:10.1016/j.cattod.2015.07.01