Staff directory Fernando Novio Vazquez

Fernando Novio Vazquez

Postdoctoral Researcher
fernando.novio(ELIMINAR)@icn2.cat
Nanostructured Functional Materials

Publications

2018

  • Dual-Fluorescent Nanoscale Coordination Polymers via a Mixed-Ligand Synthetic Strategy and Their Use for Multichannel Imaging

    Nador F., Wnuk K., García-Pardo J., Lorenzo J., Solorzano R., Ruiz-Molina D., Novio F. ChemNanoMat; 4 (2): 183 - 193. 2018. 10.1002/cnma.201700311.

    Two rationally designed strategies for covalent bonding of fluorescent dyes in coordination polymer nanoparticles aiming to achieve bifunctional fluorescent nanostructures have been developed. The first strategy was based on the synthesis of the coordination polymers structured as nanoparticles by coordination of CoII ions to two different catechol ligands containing free functional chemical groups (dopamine and 3,4-dihydroxybenzaldehyde), and a bis(imidazole)-based ligand (1,4-bis(imidazole-1-ylmethyl)benzene, bix). Subsequently, different dyes, namely fluorescein isothiocyanate (FITC), 1-pyrenebutanoic acid hydrazide (PBH) or Alexa Fluor® 568 (A568), could be sequentially attached to the surface of the nanoparticles. The second strategy was focused on the prefunctionalization of catechol ligands with the corresponding dyes and, afterwards, the coordination with the metal ions in presence of bix. In vitro studies demonstrated the internalization of the bifunctional nanoparticles and the persistence of the fluorescent properties after cell uptake without dye leaching. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim


  • Pt(IV)-based nanoscale coordination polymers: Antitumor activity, cellular uptake and interactions with nuclear DNA

    Adarsh N.N., Frias C., Ponnoth Lohidakshan T.M., Lorenzo J., Novio F., Garcia-Pardo J., Ruiz-Molina D. Chemical Engineering Journal; 340: 94 - 102. 2018. 10.1016/j.cej.2018.01.058.

    Cisplatin has been for many years the gold standard chemotherapeutic drug for the treatment of a wide range of solid tumors, even though its use is commonly associated with serious side effects including non-selective toxicity, myelosuppression or development of cisplatin resistance, among others complications. Over the last decade, a number of nanoparticle formulations were developed to reduce its side effects and improve the selectivity and efficacy of this drug. In this study, we have developed a novel nanoparticle platform based on nanoscale coordination polymer named (Zn-Pt(IV)-NCPs) which contains a Pt(IV) prodrug, Zn and the linker ligand 1,4-Bis(imidazol-1-ylmethyl)benzene (bix). The main objective has been to gain insights into the mechanism of action of this nanostructured material in comparison with cisplatin and the free Pt(IV) prodrug in order to establish a correlation between nanostructuration and therapeutic activity. Zn-Pt(IV)-NCPs nanoparticles displayed an average size close to 200 nm as determined by DLS, a good stability in physiologic environments, and a controlled drug release of Pt. In vitro studies demonstrated that Pt(IV)-NCPs showed an enhanced cytotoxic effect against cell culture of cervical cancer, neuroblastoma and human adenocarcinoma cells in comparison with free Pt(IV) prodrug. Although no difference in cell uptake of Pt was observed for any of the three cell lines assayed, a higher amount of Pt bound to the DNA was found in the cells treated with the nanostructured Pt(IV) prodrug. These studies suggest that the nanostructuration of the prodrug facilitate its activation and induce a change in the mechanism of action related to an increased interaction with the DNA as corroborated by the studies of direct interaction of the Pt(IV) prodrug, nanostructured or not, with DNA. © 2018 Elsevier B.V.


  • Solvent-Tuned Supramolecular Assembly of Fluorescent Catechol/Pyrene Amphiphilic Molecules

    Nador F., Wnuk K., Roscini C., Solorzano R., Faraudo J., Ruiz-Molina D., Novio F. Chemistry - A European Journal; 24 (55): 14724 - 14732. 2018. 10.1002/chem.201802249.

    The synthesis and structuration of a novel low-molecular-weight amphiphilic catechol compound is reported. The combination of a hydrophilic tail containing a catechol unit and a pyrene-based hydrophobic head favors solvent-tuned supramolecular assembly. Formation of hollow nanocapsules/vesicles occurs in concentrated solutions of polar protic and nonprotic organic solvents, whereas a fibril-like aggregation process is favored in water, even at low concentrations. The emission properties of the pyrene moiety allow monitoring of the self-assembly process, which could be confirmed by optical and electronic microscopy. In organic solvents and at low concentrations, this compound remains in its nonassembled monomeric form. As the concentration increases, the aggregation containing preassociated pyrene moieties becomes more evident up to a critical micellar concentration, at which vesicle-like structures are formed. In contrast, nanosized twist beltlike fibers are observed in water, even at low concentrations, whereas microplate structures appear at high concentrations. The interactions between molecules in different solvents were studied by using molecular dynamics simulations, which have confirmed different solvent-driven supramolecular interactions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim


  • Surface functionalization of metal-organic frameworks for improved moisture resistance

    Castells-Gil J., Novio F., Padial N.M., Tatay S., Ruíz-Molina D., Martí-Gastaldo C. Journal of Visualized Experiments; 2018 (139, e58052) 2018. 10.3791/58052.

    Metal-organic frameworks (MOFs) are a class of porous inorganic materials with promising properties in gas storage and separation, catalysis and sensing. However, the main issue limiting their applicability is their poor stability in humid conditions. The common methods to overcome this problem involve the formation of strong metal-linker bonds by using highly charged metals, which is limited to a number of structures, the introduction of alkylic groups to the framework by post-synthetic modification (PSM) or chemical vapour deposition (CVD) to enhance overall hydrophobicity of the framework. These last two usually provoke a drastic reduction of the porosity of the material. These strategies do not permit to exploit the properties of the MOF already available and it is imperative to find new methods to enhance the stability of MOFs in water while keeping their properties intact. Herein, we report a novel method to enhance the water stability of MOF crystals featuring Cu2(O2C)4 paddlewheel units, such as HKUST (where HKUST stands for Hong Kong University of Science & Technology), with the catechols functionalized with alkyl and fluoro-alkyl chains. By taking advantage of the unsaturated metal sites and the catalytic catecholase-like activity of CuII ions, we are able to create robust hydrophobic coatings through the oxidation and subsequent polymerization of the catechol units on the surface of the crystals under anaerobic and water-free conditions without disrupting the underlying structure of the framework. This approach not only affords the material with improved water stability but also provides control over the function of the protective coating, which enables the development of functional coatings for the adsorption and separations of volatile organic compounds. We are confident that this approach could also be extended to other unstable MOFs featuring open metal sites. © 2018, Journal of Visualized Experiments. All rights reserved.


2017

  • Ligand and solvent effects in the formation and self-assembly of a metallosupramolecular cage

    Adarsh N.N., Chakraborty A., Tarrés M., Dey S., Novio F., Chattopadhyay B., Ribas X., Ruiz-Molina D. New Journal of Chemistry; 41 (3): 1179 - 1185. 2017. 10.1039/C6NJ03456J. IF: 3.269

    Two bis-pyridyl-bis-urea ligands namely N,N′-bis-(3-pyridyl)diphenylmethylene-bis-urea (L1) and N,N′-bis-(3-picolyl)diphenylmethylene-bis-urea (L2) have been reacted with a Cu(ii) salt resulting in the formation of a metallosupramolecular cage [{Cu2(μ-L1)4(DMSO)2(H2O)2}·SO4·X] (1) and a one-dimensional coordination polymer [{Cu(1)(μ-L2)2(H2O)2}{Cu(2)(μ-L2)2(H2O)2}·2SO4·9H2O·X]n (2) (where DMSO = dimethylsulfoxide, and X = disordered lattice included solvent molecules), respectively. The single crystal structures of 1 and 2 are discussed in the context of the effect of the ligands, particularly the hydrogen bonding functionality of the ligand, on the supramolecular structural diversities observed in these metal organic compounds. The supramolecular packing of 1 is clearly influenced by the nature of the solvent and ligand used; mixtures of DMSO/MeOH or DMSO/H2O lead to the formation of blue crystals or a hydrogel, respectively. © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.


  • Surface Functionalization of Metal-Organic Framework Crystals with Catechol Coatings for Enhanced Moisture Tolerance

    Castells-Gil J., Novio F., Padial N.M., Tatay S., Ruíz-Molina D., Martí-Gastaldo C. ACS Applied Materials and Interfaces; 9 (51): 44641 - 44648. 2017. 10.1021/acsami.7b15564. IF: 7.504

    Robust catechol coatings for enhanced moisture tolerance were produced in one step by direct reaction of Hong Kong University of Science and Technology (HKUST) with synthetic catechols. We ascribe the rapid formation of homogeneous coatings around the metal-organic framework particles to the biomimetic catalytic activity of Cu(II) dimers in the external surface of the crystals. Use of fluorinated catechols results in hydrophobic, permeable coatings that protect HKUST from water degradation while retaining close to 100% of its original sorption capacity. © 2017 American Chemical Society.


  • Synthesis and Characterization of PtTe2 Multi-Crystallite Nanoparticles using Organotellurium Nanocomposites

    Fernández-Lodeiro J., Rodríguez-Gónzalez B., Novio F., Fernández-Lodeiro A., Ruiz-Molina D., Capelo J.L., Santos A.A.D., Lodeiro C. Scientific Reports; 7 (1, 9889) 2017. 10.1038/s41598-017-10239-8. IF: 4.259

    Herein, we report the synthesis of new PtTe2 multi-crystallite nanoparticles (NPs) in different sizes through an annealing process using new nanostructured Pt-Te organometallic NPs as a single source precursor. This precursor was obtained in a single reaction step using Ph2Te2 and H2PtCl6 and could be successfully size controlled in the nanoscale range. The resulting organometallic composite precursor could be thermally decomposed in 1,5 pentanediol to yield the new PtTe2 multi-crystallite NPs. The final size of the multi-crystallite spheres was successfully controlled by selecting the nanoprecursor size. The sizes of the PtTe2 crystallites formed using the large spheres were estimated to be in the range of 2.5-6.5 nm. The results provide information relevant to understanding specific mechanistic aspects related to the synthesis of organometallic nanomaterials and nanocrystals based on platinum and tellurium. © 2017 The Author(s).


2016

  • Coordination polymers build from 1,4-bis(imidazol-1yl-methyl)benzene: From Crystalline to Amorphous

    N. N Adarsh, F. Novio, D. Ruiz-Molina Dalton Transactions; 45 (28): 11233 - 11255. 2016. 10.1039/C6DT01157H. IF: 4.177

    The supramolecular chemistry of the bis-imidazole ligand 1,4-bis(imidazol-1-ylmethyl)benzene, popularly known as bix, has been explored by various researchers in order to synthesize functional coordination polymers (CPs). The flexibility of the bix ligand, its unpredictable conformation and its coordination behaviour with transition metal ions have resulted in a huge number of structurally diverse and functionally intriguing CPs. In this perspective review we discuss the progress in CPs of bix between 1997 and today. More precisely, this review emphasizes the developments in functional supramolecular coordination polymers built from the bix ligand, from crystalline materials to amorphous nanomaterials.


  • Nanoscale coordination polymers obtained in ultrasmall liquid droplets on solid surfaces and its comparison to different synthetic volume scales

    Bellido E., González-Monje P., Guardingo M., Novio F., Sánchez A., Montero M., Molnar G., Bousseksou A., Ruiz-Molina D. RSC Advances; 6 (80): 76666 - 76672. 2016. 10.1039/c6ra14368g. IF: 3.289

    Synthesis of coordination polymers at femtolitre scales assisted by an AFM tip has become an area of increasing interest due to the astonishing range of implications that derive from it, from gaining basic knowledge of confined reactions in femtolitre droplets to the fabrication of molecular-based devices. However, this field is still in its infancy, a reason why several new basic studies that allow us control over it are highly required. Herein we report the synthesis of [Co(CH3COO)2(μ-4,4′-bpy)] in femtolitre droplets on surfaces and the results are compared with those obtained for the same reaction at different volume scales. ©2016 The Royal Society of Chemistry.


  • Switchable colloids, thin-films and interphases based on metal complexes with non-innocent ligands: The case of valence tautomerism and their applications

    Vázquez-Mera N.A., Novio F., Roscini C., Bellacanzone C., Guardingo M., Hernando J., Ruiz-Molina D. Journal of Materials Chemistry C; 4 (25): 5879 - 5889. 2016. 10.1039/c6tc00038j. IF: 5.066

    Successful nanostructuration approaches developed in the last few years have allowed the preparation of robust valence tautomeric (VT) switchable (micro-/nano-) structures of a variety of dimensions and morphologies. These results are expected to definitely foster the implementation of these materials on hybrid molecular electronic devices but also endorse new applications in other different fields such as sensing, drug delivery or water remediation, among others. © The Royal Society of Chemistry 2016.


  • Synthesis of Nanoscale Coordination Polymers in Femtoliter Reactors on Surfaces

    Guardingo M., González-Monje P., Novio F., Bellido E., Busqué F., Molnár G., Bousseksou A., Ruiz-Molina D. ACS Nano; 10 (3): 3206 - 3213. 2016. 10.1021/acsnano.5b05071. IF: 13.334

    In the present work, AFM-assisted lithography was used to perform the synthesis of a coordination polymer inside femtoliter droplets deposited on surfaces. For this, solutions of the metal salt and the organic ligand were independently transferred to adjacent tips of the same AFM probe array and were sequentially delivered on the same position of the surface, creating femtoliter-sized reaction vessels where the coordination reaction and particle growth occurred. Alternatively, the two reagents were mixed in the cantilever array by loading an excess of the inks, and transferred to the surface immediately after, before the precipitation of the coordination polymer took place. The in situ synthesis allowed the reproducible obtaining of round-shaped coordination polymer nanostructures with control over their XY positioning on the surface, as characterized by microscopy and spectroscopy techniques. © 2016 American Chemical Society.


2015

  • Covalent Grafting of Coordination Polymers on Surfaces: The Case of Hybrid Valence Tautomeric Interphases

    González-Monje P., Novio F., Ruiz-Molina D. Chemistry - A European Journal; 21 (28): 10094 - 10099. 2015. 10.1002/chem.201500671. IF: 5.731

    We have developed a novel approach for grafting coordination polymers, structured as nanoparticles bearing surface reactive carboxylic groups, to amino-functionalized surfaces through a simple carbodiimide-mediated coupling reaction. As a proof-of-concept to validate our approach, and on the quest for novel hybrid interphases with potential technological applications, we have used valence tautomeric nanoparticles exhibiting spin transition at or around room temperature. SEM and AFM characterization reveal that the nanoparticles were organized chiefly into a single monolayer while X-ray photoelectron spectroscopy (XPS) measurements confirm that the nanoparticles retain a temperature-induced electronic redistribution upon surface anchorage. Our results represent an effective approach towards the challenging manufacture of coordination polymers. CPPs immobilization: A generic approach for immobilizing coordination polymer nanoparticles (CPPs) on gold surfaces is reported. The protocol involves covalent bonding between amino-terminated alkyl chains on the gold surface and carboxylic groups on the CPPs surface. The thickness of the nanoparticle monolayer is comparable to the nanoparticle size. The nanoparticles used exhibit valence tautomerism in bulk and keep this property after surface attachment, as corroborated by X-ray photoelectron spectroscopy (XPS) measurements. The results represent an effective approach towards the manufacture of coordination polymers. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.


  • Design and Synthesis of a Noninnocent Multitopic Catechol and Pyridine Mixed Ligand: Nanoscale Polymers and Valence Tautomerism

    Guardingo M., Busqué F., Novio F., Ruiz-Molina D. Inorganic Chemistry; 54 (14): 6776 - 6781. 2015. 10.1021/acs.inorgchem.5b00598. IF: 4.762

    The design and synthesis of a new redox-active ligand combining catechol and pyridine units have allowed the achievement of cobalt-based nanoscale coordination polymer particles in a single-step exhibiting a switchable valence tautomeric behavior and thermal hysteresis. The combination of polymerizing capabilities with redox-active responses in a unique ligand leads to the formation of nanoparticles exhibiting a gradual valence tautomeric interconversion in the 35-370 K temperature range. Using one single ligand to obtain these nanoparticles facilitates possible nanostructure formation methodologies. (Chemical Equation Presented). © 2015 American Chemical Society.


  • Dual T1/T2 MRI contrast agent based on hybrid SPION@coordination polymer nanoparticles

    Borges M., Yu S., Laromaine A., Roig A., Suárez-García S., Lorenzo J., Ruiz-Molina D., Novio F. RSC Advances; 5 (105): 86779 - 86783. 2015. 10.1039/c5ra17661a. IF: 3.840

    We report a novel hybrid T1/T2 dual MRI contrast agent by the encapsulation of SPIONs (T2 contrast agent) into an iron-based coordination polymer with T1-weighted signal. This new hybrid material presents improved relaxometry and low cytotoxicity, which make it suitable for its use as contrast agent for MRI. © 2015 The Royal Society of Chemistry.