Staff directory
Fernando Novio Vázquez
Visiting Senior Researcher
Universitat Autònoma de Barcelona (UAB)
fernando.novio(ELIMINAR)@icn2.cat
Nanostructured Functional Materials
Publications
2017
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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.
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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.
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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
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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.
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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.
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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.
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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
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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.
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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.
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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.
2014
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Amorphous Coordination Polymer Particles for Biomedicine
Novio F., Ruiz-Molina D., Lorenzo J. Bio- and Bioinspired Nanomaterials; 9783527335817: 113 - 138. 2014. 10.1002/9783527675821.ch05.
This chapter focuses on a specific class of coordination polymeric materials with different dimensionality, but with an amorphous superstructure. The terminology coordination polymer particles (CPPs) is used to designate the new emergent class of amorphous nanoparticles with highly tailorable size and properties that open up new perspectives in different fields, especially in medicine. The chapter outlines the most recent advances in the synthesis, characterization, and properties of CPPs with a high potential to be used as multifunctional platforms for theranostics, including smart drug-delivery systems, active nanostructures for bioimaging, or a combination of both. It compiles currently considerable effort to incorporate theranostics functions into a single nanoscale system for the more effective treatment of medical diseases, especially cancer. The chapter summarizes the most interesting coordination polymer nanodevices in the field of medicine, from encapsulation and drug delivery to bioimaging and sensing. © 2015 Wiley-VCH Verlag GmbH & Co. KGaA. All rights reserved.
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Bio- and Bioinspired Nanomaterials
Ruiz-Molina D., Novio F., Roscini C. Bio- and Bioinspired Nanomaterials; 9783527335817: 1 - 457. 2014. 10.1002/9783527675821.
A comprehensive overview of nanomaterials that are inspired by or targeted at biology, including some of the latest breakthrough research. Throughout, valuable contributions from top-level scientists illustrate how bionanomaterials could lead to novel devices or structures with unique properties. The first and second part cover the most relevant synthetic and bioinspired nanomaterials, including surfaces with extreme wettability properties, functional materials with improved adhesion or structural and functional systems based on the complex and hierarchical organization of natural composites. These lessons from nature are explored in the last section where bioinspired materials are proposed for biomedical applications, showing their potential for future applications in drug delivery, theragnosis, and regenerative medicine. A navigational guide aimed at advanced and specialist readers, while equally relevant for readers in research, academia or private companies focused on high added-value contributions. Young researchers will also find this an indispensable guide in choosing or continuing to work in this stimulating area, which involves a wide range of disciplines, including chemistry, physics, materials science and engineering, biology, and medicine. © 2015 Wiley-VCH Verlag GmbH & Co. KGaA. All rights reserved.