Open Access
Consecutive single-crystal-to-single-crystal isomerization of novel octamolybdate anions within a microporous hybrid framework with robust water sorption properties
(Wiley, 2023) Ruiz Bilbao, Estíbaliz; Iturrospe, Amaia; Reinoso, Santiago; Artetxe, Beñat; Beobide, Garikoitz; San Felices, Leire; Lezama, Luis; Gutiérrez Zorrilla, Juan M.; Darwish, Shaza; Sensharma, Debobroto; Zaworotko, Michael J.; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2
The 3D hybrid framework [{Cu(cyclam)}3(kMo8O27)]· 14H2O (1) (cyclam=1,4,8,11-tetraazacyclotetradecane) undergoes sequential single-crystal-to-singlecrystal transformations upon heating to afford two different anhydrous phases (2 a and 3a). These transitions modify the framework dimensionality and enable the isomerization of k-octamolybdate (k-Mo8) anions into λ (2 a) and μ (3 a) forms through metal migration. Hydration of 3 a involves condensation of one water molecule to the cluster to afford the γ-Mo8 isomer in 4, which dehydrates back into 3a through the 6a intermediate. In contrast, 2a reversibly hydrates to form 5, exhibiting the same Mo8 cluster as that of 1. It is remarkable that three of the Mo8 clusters (k, λ and μ) are new and that up to three different microporous phases can be isolated from 1 (2 a, 3a, and 6a). Water vapor sorption analyses show high recyclability and the highest uptake values for POM-based systems. The isotherms display an abrupt step at low humidity level desirable for humidity control devices or water harvesting in drylands.
Open Access
Polioxometalatoak ingurune urtsuan: egitura esanguratsuenak
(Universidad de País Vasco, 2021) Ruiz-Bilbao, E.; Fernández Navarro, Leticia; Artetxe, Beñat; San-Felices, L.; Reinoso, Santiago; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2
Polioxometalatoen (POMen) konposizio eta egitura aniztasun ikaragarria, ur disoluzioan aurkezten dituzten oreka kimiko dinamikoen emaitza dira. Izan ere, beraien eraketa prozesuak ingurune azidotan gertatzen diren oxoanioien kondentsazio konplexuetan oinarrituta daude eta ondorioz, pH baldintza jakinetan zenbait metal-oxigeno kluster ezberdin daude orekan. Hortaz, POMei dagozkien topologia garrantzitsuenen ikuspegi orokorra aurkezten da lan honetan, pHaren arabera ur disoluzioan agertzen diren espezie nagusiei erreparatuz. Lehenik, ohiko iso- eta hetero-polioxobanadato, -polioxomolibdato eta ¿polioxowolframatoak aztertu dira eta bukatzeko hain konbentzionalak ez diren POM familietan jarri da arreta; hala nola, molibdato erraldoiak, uranio peroxo-klusterrak eta metal noblez osatutako egiturak..
Open Access
Polyoxometalates in catalysis
(Jenny Stanford Publishing, 2022) Alcañiz Monge, Juan; Reinoso, Santiago; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2
This chapter will focus on providing a basis for understanding the mechanisms involved in the catalysis carried out by selected polyoxometalate (POM)-based compounds. The catalysts discussed herein will be either insoluble POM salts or POM clusters heterogenized on porous solid supports, including activated carbon materials and metallic oxides such as zirconia. The influence on the catalytic activity of both the POM catalytic species and the active porous support will be the main aspects to be commented and analyzed in detail within the chapter.
Open Access
Gold nanoparticles capped with a novel titanium(iv)-containing polyoxomolybdate cluster: selective and enhanced bactericidal effect against Escherichia coli
(Wiley, 2024) Paesa, Mónica; Almazán, Fernando; Yus Argón, Cristina; Sebastián, Víctor; Arruebo Gordo, Manuel; Reinoso, Santiago; Pellejero, Ismael; Gandía Pascual, Luis; Mendoza, Gracia; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa
Bacterial infections are a public health threat of increasing concern in medical care systems; hence, the search for novel strategies to lower the use of antibiotics and their harmful effects becomes imperative. Herein, the antimicrobial performance of four polyoxometalate (POM)-stabilized gold nanoparticles (Au@POM) against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) as Gram-negative and Gram-positive bacteria models, respectively, is studied. The bactericidal studies performed, both in planktonic and sessile forms, evidence the antimicrobial potential of these hybrid nanostructures with selectivity toward Gram-negative species. In particular, the Au@GeMoTi composite with the novel [Ti2(HGeMo7O28)2]10¿ POM capping ligand exhibits outstanding bactericidal efficiency with a minimum inhibitory concentration of just 3.12 µm for the E. coli strain, thus outperforming the other three Au@POM counterparts. GeMoTi represents the fourth example of a water-soluble TiIV-containing polyoxomolybdate, and among them, the first sandwich-type structure having heteroatoms in high-oxidation state. The evaluation of the bactericidal mechanisms of action points to the cell membrane hyperpolarization, disruption, and subsequent nucleotide leakage and the low cytotoxicity exerted on five different cell lines at antimicrobial doses demonstrates the antibiotic-like character. These studies highlight the successful design and development of a new POM-based nanomaterial able to eradicate Gram-negative bacteria without damaging mammalian cells.

Reinoso, Santiago

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