Anticancer applications of nanostructured silica-based materials functionalized with titanocene derivatives: Induction of cell death mechanism through TNFR1 modulation

This article belongs to the Special Issue Nanomaterials for Biomedical ApplicationsA series of cytotoxic titanocene derivatives have been immobilized onto nanostructured silica-based materials using two different synthetic routes, namely, (i) a simple grafting protocol via protonolysis of the Ti-Cl bond; and (ii) a tethering method by elimination of ethanol using triethoxysilyl moieties of thiolato ligands attached to titanium. The resulting nanostructured systems have been characterized by different techniques such as XRD, XRF, DR-UV, BET, SEM, and TEM, observing the incorporation of the titanocene derivatives onto the nanostructured silica and slight changes in the textural features of the materials after functionalization with the metallodrugs. A complete biological study has been carried out using the synthesized materials exhibiting moderate cytotoxicity in vitro against three human hepatic carcinoma (HepG2, SK-Hep-1, Hep3B) and three human colon carcinomas (DLD-1, HT-29, COLO320) and very low cytotoxicity against normal cell lines. In addition, the cells' metabolic activity was modified by a 24-h exposure in a dose-dependent manner. Despite not having a significant effect on TNFalfa or the proinflammatory interleukin 1alfa secretion, the materials strongly modulated tumor necrosis factor (TNF) signaling, even at sub-cytotoxic concentrations. This is achieved mainly by upregulation of the TNFR1 receptor production, something which has not previously been observed for these systems.We gratefully acknowledge financial support from FEDER and the Ministerio de Economía y Competitividad, Spain (grant no. CTQ2015-66164-R) and the Romanian UEFISCDI Exploratory Research Project PN-III-P4-ID-PCE-2016-0870, IMPRESS. We would also like to thank Universidad Rey Juan Carlos and Banco de Santander for supporting our Research Group of Excellence QUINANOAP. Finally, we thank D. Pérez for valuable discussion and S. Carralero and C. Forcé for their assistance with solid-state NMR experiments

Poly[diaqua-μ2-oxalato-di-μ2-pyrimidine-2-carboxyl­ato-dimanganese(II)]

In the title compound, [Mn2(C2O4)(C5H3N2O2)2(H2O)2]n, the MnII atom exhibits a distorted octa­hedral coordination geometry, with the centrosymmetric oxalate anion and the monoanionic pyrimidine-2-carboxyl­ate ligands generating a two-dimensional honeycomb network with a (6,3)-topology

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

Divergent responses to thermogenic stimuli in BAT and subcutaneous adipose tissue from interleukin 18 and interleukin 18 receptor 1-deficient mice

Brown and beige adipocytes recruitment in brown (BAT) or white adipose tissue, mainly in the inguinal fat pad (iWAT), meet the need for temperature adaptation in cold-exposure conditions and protect against obesity in face of hypercaloric diets. Using interleukin18 (Il18) and Il18 receptor 1- knockout (Il18r1-KO) mice, this study aimed to investigate the role of IL18 signaling in BAT and iWAT activation and thermogenesis under both stimuli. Il18-KO, extremely dietary obesity-prone as previously described, failed to develop diet-induced thermogenesis as assessed by BAT and iWAT Ucp1 mRNA levels. Overweight when fed standard chow but not HFD, HFD-fed Il18r1-KO mice exhibited increased iWAT Ucp1 gene expression. Energy expenditure was reduced in pre-obese Il18r1-KO mice and restored upon HFD-challenge. Cold exposure lead to similar results; Il18r1-KO mice were protected against acute body temperature drop, displaying a more brown-like structure, alternative macrophage activation and thermogenic gene expression in iWAT than WT controls. Opposite effects were observed in Il18-KO mice. Thus, Il18 and Il18r1 genetic ablation disparate effects on energy homeostasis are likely mediated by divergent BAT responses to thermogenic stimuli as well as iWAT browning. These results suggest that a more complex receptor-signaling system mediates the IL18 adipose-tissue specific effects in energy expenditure.This work has been supported by European Community (FP7/2007n° 245009: “NeuroFAST”), Ministerio de Economía y Competitividad (PP and MCGG: BFU2007–62683/BFI and PP, MCGG and CD: CIBERobn (CB06/03)) and Xunta de Galicia Grants (MCGG and LL: PGIDIT06PXIB208067PR and GPC2014/030). CIBER de Fisiopatología de la Obesidad y Nutrición is an initiative of ISCIIIS

2D-cadmium MOF and gismondine-like zinc coordination network based on the N-(2-tetrazolethyl)-4′-glycine linker

We have designed and synthesized two new metal-organic-frameworks (MOFs) using the novel N-(2-tetrazolethyl)-4′-glycine spacer (TeGly)2−. These materials exhibit intense photoluminescence.This work was supported by the MEC of Spain (Project CTQ2011-24478) and the Junta de Andalucía (FQM-1484). D. F.-J. thanks the Royal Society for a University Research Fellowship.This is the author accepted manuscript. The final version is available from the Royal Society of Chemistry via http://dx.doi.org/10.1039/C5NJ00011

Through-space hopping transport in an iodine-doped perylene-based metal-organic framework

Electrically conductive metal-organic frameworks (MOFs) have emerged in the past few years as promising materials towards applications in (opto)electronics, electrocatalysis and energy storage, among others. One of the most common strategies for the design of conductive MOFs is based on the use of electroactive organic ligands and their partial oxidation/reduction to increase the number of charge carriers. Although perylene salts were reported as the first molecular conductors, they have been scarcely explored as building blocks for the construction of conductive MOFs. Herein we report the electrical conductivity enhancement of a microporous perylene-based MOF upon partial ligand oxidation by using two-probe single-crystal devices. The origin of the conductivity enhancement is rationalised by means of spectroscopic studies and quantum-chemical calculations, supporting a through-space hopping transport along the herringbone perylene packing. This study opens the way for the design of conductive MOFs based on perylene building blocks.This work was developed within the scope of the project CICECO-Aveiro Institute of Materials, Grants UIDB/50011/2020 and UIDP/50011/2020, financed by national funds through the FCT/MEC and when appropriate co-financed by FEDER under the PT2020 Partnership Agreement. We thank FCT for funding the project PTDC/QUI-ELT/2593/2021. We acknowledge Spanish government (PID2020-119748GA-I00, funded by MICIN/AEI/10.13039/501100011033, and the Maria de Maeztu CEX2019-000919-M grant) and Generalitat Valenciana (GV/2021/027, GVPROMETEO2020-077). G. V. is grateful to FCT for a PhD grant (2020.08520.BD). A. P. is grateful to FCT for a PhD grant (2020.06159.BD). FCT is also acknowledged by M. I. for a Junior Researcher Position (CEECIND/00546/2018). We thank Celeste Azevedo for TGA and Raman measurements. We thank Prof. Luís Carlos and Prof. Carlos Brites (Phantom-G) for the use and assistance with spectrofluorimeter and quantum yield equipment. We thank Prof. Nikolai Sobolev for EPR measurements

Through-space hopping transport in an iodine-doped perylene-based metal–organic framework

Electrically conductive metal-organic frameworks (MOFs) have emerged in the past few years as promising materials towards applications in (opto)electronics, electrocatalysis and energy storage, among others. One of the most common strategies for the design of conductive MOFs is based on the use of electroactive organic ligands and their partial oxidation/reduction to increase the number of charge carriers. Although perylene salts were reported as the first molecular conductors, they have been scarcely explored as building blocks for the construction of conductive MOFs. Herein we report the electrical conductivity enhancement of a microporous perylene-based MOF upon partial ligand oxidation by using two-probe single-crystal devices. The origin of the conductivity enhancement is rationalised by means of spectroscopic studies and quantum-chemical calculations, supporting a through-space hopping transport along the herringbone perylene packing. This study opens the way for the design of conductive MOFs based on perylene building blocks.publishe

Interpenetrated Luminescent Metal-Organic Frameworks based on 1H-Indazole-5-carboxylic Acid

Herein we report the formation and characterization of two novel Zn-based multifunctional metal-organic frameworks (MOFs) based on 1H-indazole-5-carboxylic acid and bipyridine-like linkers, synthesized by soft solvothermal routes. These materials possess isoreticular 2-fold interpenetrated three-dimensional structures that afford a flexible character and allow porosity modulation of the MOFs as confirmed by CO2 sorption measurements. Apart from this attractive structural feature, the MOFs exhibit fascinating luminescent properties involving both luminescence thermometry and long-lasting phosphorescence

Multifunctional Lanthanide-Based Metal−Organic Frameworks Derived from 3‑Amino-4-hydroxybenzoate: Single-Molecule Magnet Behavior, Luminescent Properties for Thermometry, and CO2 Adsorptive Capacity

ACKNOWLEDGMENTS The authors thank SGIker of UPV/EHU and European funding (ERDF and ESF) for technical and human support as well as wish to acknowledge the terrific help of all reviewers of the present manuscript whose comments helped to improve the quality of the work.Supporting Information The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.inorgchem.2c00544.Funding E.E. is grateful to the Government of the Basque Country for the predoctoral fellowship and R.F.M. to the Junior Research Position CEECIND/ 00553/2017. The research contract of FF (REF-168-89-ARH/2018) is funded by national funds (OE), through FCT, in the scope of the framework contract foreseen in nos. 4, 5, and 6 of article 23 of the Decree-Law 57/2016, of 29 August, changed by Law 57/2017, of 19 July. This work was developed within the scope of the projects given by the Spanish Ministry of Science, Innovation and Universities (MCIU/AEI/ FEDER, UE) (PGC2018-102052-A-C22, PGC2018-102052-BC21, and PID2019-108028GB-C21), Gobierno Vasco/Eusko Jaurlaritza (IT1310-19 and IT1291-19), Junta de Andalucía (FQM-394), University of the Basque Country (GIU 20/028), and CICECO-Aveiro Institute of Materials (UIDB/50011/ 2020 and UIDP/50011/2020).Herein, we describe and study a new family of isostructural multifunctional metal–organic frameworks (MOFs) with the formula {[Ln5L6(OH)3(DMF)3]·5H2O}n (where (H2L) is 3-amino-4-hydroxybenzoic acid ligand) for magnetism and photoluminescence. Interestingly, three of the materials (Dy-, Er-, and Yb-based MOFs) present single-molecule magnet (SMM) behavior derived from the magnetic anisotropy of the lanthanide ions as a consequence of the adequate electronic distribution of the coordination environment. Additionally, photoluminescence properties of the ligand in combination with Eu and Tb counterparts were studied, including the heterometallic Eu–Tb mixed MOF that shows potential as ratiometric luminescent thermometers. Finally, the porous nature of the framework allowed showing the CO2 sorption capacity.Government of the Basque CountryJunior Research Position CEECIND/ 00553/2017National funds (OE)Spanish Ministry of Science, Innovation and Universities (MCIU/AEI/ FEDER, UE) (PGC2018-102052-A-C22, PGC2018-102052-BC21, and PID2019-108028GB-C21)Gobierno Vasco/Eusko Jaurlaritza (IT1310-19 and IT1291-19)Junta de Andalucía (FQM-394)University of the Basque Country (GIU 20/028)CICECO-Aveiro Institute of Materials (UIDB/50011/ 2020 and UIDP/50011/2020

Global distribution of two fungal pathogens threatening endangered sea turtles

This work was supported by grants of Ministerio de Ciencia e Innovación, Spain (CGL2009-10032, CGL2012-32934). J.M.S.R was supported by PhD fellowship of the CSIC (JAEPre 0901804). The Natural Environment Research Council and the Biotechnology and Biological Sciences Research Council supported P.V.W. The funders had no role in study design, data collection and analysis, decision to publish, or preparation of the manuscript. Thanks Machalilla National Park in Ecuador, Pacuare Nature Reserve in Costa Rica, Foundations Natura 2000 in Cape Verde and Equilibrio Azul in Ecuador, Dr. Jesus Muñoz, Dr. Ian Bell, Dr. Juan Patiño for help and technical support during samplingPeer reviewedPublisher PD