2D-Coordination polymers based on 1H-indazole4-carboxylic acid and transition metal ions: magnetic, luminescence and biological properties

We report the formation of five novel multifunctional coordination polymers based on 1H-indazole-4- carboxylic acid (HL). To the best of our knowledge, these complexes are the first examples of coordination compounds constructed with this interesting ligand. These materials were synthesized by solvothermal routes, possess different 2D-structures and show interesting magnetic properties due to the copper compound showing an unusual spin-canted effect while the anisotropic cobalt material behaves as a fieldinduced single molecule magnet. MTT assays performed on human embryonic kidney (HEK293) and mouse skin melanoma (B16-F10) cell lines indicated that the Cd-based compound was the only one exhibiting dose-dependent toxicity on B16-F10 cells, most likely due to the release of toxic Cd(II). Cadmium and zinc polymers exhibit interesting luminescence properties. The fact that zinc polymers did not exhibit inherent toxicity against both cancer and non-cancerous cells make this new family an excellent candidate for further investigation in the field of luminescent materials with biomedical applications.Junta de Andalucia FQM-394 FQM-1484Red Guipuzcoana de Ciencia, Tecnologia e Innovacion OF218/2018University of Basque Country GIU 17/13Basque Government IT1005-16Spanish Ministry of Science, Innovation and Universities (MCIU/AEI/FEDER, UE) PGC2018-102052-A-C22 PGC2018-102052-B-C21Junta de Andalucia FQM-394 FQM-1484European Union (EU)ESFGovernment of the Basque CountryFEDER/MCIU/AEI RYC-2016-21042 JdC-201

Espacio y territorios: razón, pasión e imaginarios

En este caleidoscopio de acercamientos hacia lo espacial y territorial, las visiones se mueven desde aquellas románticas y existencialistas, pasando por aquellas objetivistas y positivistas, hasta las estructuralistas y postestructuralistas. Por el espacio y el territorio se interesan con enfoques diversos numerosas disciplinas, desde la psicología, la etología o la literatura, y las ciencias naturales como la biología o la ecología, hasta las ciencias sociales y políticas, como la geografía, la antropología, la economía y la sociología. Este interés multidisciplinario demuestra la importancia y la complejidad del tema espacial y territorial, y reclama la necesidad de su estudio y comprensión interdisciplinarios, como se intenta con esta publicación

Photoluminescent Coordination Polymers Based on Group 12 Metals and 1H-Indazole-6-Carboxylic Acid

Two new coordination polymers (CPs) based on Zn(II) and Cd(II) and 1H-indazole-6- carboxylic acid (H2L) of general formulae [Zn(L)(H2O)]n (1) and [Cd2 (HL)4 ]n (2) have been synthesized and fully characterized by elemental analyses, Fourier transformed infrared spectroscopy and single crystal X-ray diffraction. The results indicate that compound 1 possesses double chains in its structure whereas 2 exhibits a 3D network. The intermolecular interactions, including hydrogen bonds, C–H···π and π···π stacking interactions, stabilize both crystal structures. Photoluminescence (PL) properties have shown that compounds 1 and 2 present similar emission spectra compared to the free-ligand. The emission spectra are also studied from the theoretical point of view by means of time-dependent density-functional theory (TD-DFT) calculations to confirm that ligand-centred π-π* electronic transitions govern emission of compound 1 and 2. Finally, the PL properties are also studied in aqueous solution to explore the stability and emission capacity of the compounds

Photoluminescent coordination polymers based on group 12 metals and 1h-indazole-6-carboxylic acid.

Two new coordination polymers (CPs) based on Zn(II) and Cd(II) and 1H-indazole-6-carboxylic acid (H L) of general formulae [Zn(L)(H O)] (1) and [Cd (HL) ] (2) have been synthe-sized and fully characterized by elemental analyses, Fourier transformed infrared spectroscopy and single crystal X-ray diffraction. The results indicate that compound 1 possesses double chains in its structure whereas 2 exhibits a 3D network. The intermolecular interactions, including hydrogen bonds, C–H···π and π···π stacking interactions, stabilize both crystal structures. Photoluminescence (PL) properties have shown that compounds 1 and 2 present similar emission spectra compared to the free-ligand. The emission spectra are also studied from the theoretical point of view by means of time-dependent density-functional theory (TD-DFT) calculations to confirm that ligand-centred π-π* electronic transitions govern emission of compound 1 and 2. Finally, the PL properties are also studied in aqueous solution to explore the stability and emission capacity of the compounds.Financial support was given by Junta de Andalucía (Spain) (FQM-394), University of the Basque Country (GIU 17/13), Gobierno Vasco/Eusko Jaurlaritza (IT1005-16), and the Spanish Ministry of Science, Innovation and Universities (MCIU/AEI/FEDER, UE) (PGC2018-102052-A-C22, PGC2018-102052-B-C21). J.M.D.L. and G.B.R.R. acknowledge the FEDER/MCIU/AEI for their Ramón y Cajal (RYC-2016-21042) and Juan de la Cierva (JdC-2017) fellowships, respectively. S.R. acknowledges the Juan de la Cierva Incorporación Fellowship (grant agreement no. IJC2019-038894-I). E.E.-E. is grateful to the Government of the Basque Country for the predoctoral fellowship. The authors thank for technical and human support provided by SGIker of UPV/EHU and European funding (ERDF and ESF)

Multifunctional nanomaterials for biofortification and protection of tomato plants

Calcium phosphate nanoparticles were doped with zinc ions to produce multifunctional nanomaterials for efficient agronomic fortification and protection of plants. The resulting round-shaped nanoparticles (nanoZn) were composed of 20.3 wt % Ca, 14.8 wt % P, and 13.4 wt % Zn and showed a pH-controlled solubility. NanoZn were stable in aqueous solutions at neutral pH but dissolved in citric acid at pH 4.5 (i.e., the pH inside tomato fruits), producing a pH-responsive delivery of the essential nutrients Ca, P, and Zn. In fact, the foliar application of nanoZn on tomato plants provided tomatoes with the highest Zn, Ca, and P contents (causing, respectively, a 65, 65, and 15% increase with respect to a conventional treatment with ZnSO4) and the highest yields. Additionally, nanoZn (100 ppm of Zn) inhibited in vitro the growth of Pseudomonas syringae (Ps), the main cause of bacterial speck, and significantly reduced Ps incidence and mortality in tomato seeds, previously inoculated with the pathogen. Therefore, nanoZn present dual agricultural applicability, enriching crops with nutrients with important metabolic functions in humans and simultaneously protecting the plants against important bacterial-based diseases, with considerable negative impact in crop production.This work has been performed thanks to the funding of the Junta de Andalucía through the project NanoFERTI (P18-TP-969) and projects NanoFERTI2 (CPP2021-008801) and nanoSOP (PDC2022-133191-I00) funded by MCIN/AEI/10.13039/501100011033 and NextGenerationEU/PRTR. G.B.R.-R. also acknowledge grant RYC2021-032734-I funded by MCIN/AEI/10.13039/501100011033 and by “European Union NextGenerationEU/PRTR”.Peer reviewe

Supplementary information for Multifunctional nanomaterials for biofortification and protection of tomato plants

Details of analytical methods validation (Section S1); scale-up and cost reduction of nanoZn synthesis (Section S2); additional material characterization (Figures S1–S3); additional photograph of plant leaves after the treatments (Figure SI4); additional information on Ps growth (Figure SI5); characterization of low-cost nanoparticles (Figure SI6); conditions of bacterial growth and RDA of zinc, respectively (Tables SI1 and SI2).Peer reviewe

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, 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 real-time 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. lactis