Staff directory
Fernando Novio Vázquez
Visiting Senior Researcher
Universitat Autònoma de Barcelona (UAB)
fernando.novio(ELIMINAR)@icn2.cat
Nanostructured Functional Materials
Publications
2021
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Antitumour activity of coordination polymer nanoparticles
Suárez-García S., Solórzano R., Alibés R., Busqué F., Novio F., Ruiz-Molina D. Coordination Chemistry Reviews; 441 (213977) 2021. 10.1016/j.ccr.2021.213977. IF: 22.315
Nanoscale coordination polymers (NCPs) have fascinated researchers over the last years. Their intrinsic theranostic properties of metal ions and organic ligands, the encapsulation of several drugs/biomolecules with excellent yields and the surface functionalisation, enhancing their biocompatibility and targeting, have remarkably impacted in prospective drug delivery alternatives in medicine. Moreover, the properties and characteristics of these nanoparticles (NPs) can be fine-tuned thanks to the synthetic flexibility of coordination chemistry. For all these reasons, the number of examples published has grown exponentially over the last years, embracing different disciplines such as molecular electronics, sensors or nanomedicine, among others. Specifically, significant advances in antitumoural applications are reported, one of the areas where this novel family of NPs has experienced a considerable advance. NCPs have accomplished a high sophistication degree and efficiency as theranostic nanoplatforms (i.e., drug delivery carriers and bioimaging probes) with long residence time in the bloodstream, targeting capacities and remarkable cellular internalisation. In this review, an introduction emphasizing the advantages of NPs for cancer treatment is included. Later on, the most representative examples of NCPs for antitumoural applications are described grouped into six mean representative areas: i) encapsulation approaches, ii) stimuli-responsive NCPs, iii) metal chemotherapy, iv) photodynamic therapy (PDT), v) unconventional therapeutic approaches and vi) theranostics. Particular emphasis is given to understand the encapsulation/release properties of these particles at the nanoscale and their interaction with biological environments, highlighting any limitation and challenges that these systems are facing from a clinical translation perspective and envisioning possible future trends and areas that will deserve further attention for the following years. © 2021 The Authors
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Bioinspired theranostic coordination polymer nanoparticles for intranasal dopamine replacement in parkinson's disease
García-Pardo J., Novio F., Nador F., Cavaliere I., Suárez-García S., Lope-Piedrafita S., Candiota A.P., Romero-Gimenez J., Rodríguez-Galván B., Bové J., Vila M., Lorenzo J., Ruiz-Molina D. ACS Nano; 15 (5): 8592 - 8609. 2021. 10.1021/acsnano.1c00453. IF: 15.881
Dopamine (DA) is one of the main neurotransmitters found in the central nervous system and has a vital role in the function of dopaminergic (DArgic) neurons. A progressive loss of this specific subset of cells is one of the hallmarks of age-related neurodegenerative disorders such as Parkinson's disease (PD). Symptomatic therapy for PD has been centered in the precursor l-DOPA administration, an amino acid precursor of DA that crosses the blood-brain barrier (BBB) while DA does not, although this approach presents medium- to long-term side effects. To overcome this limitation, DA-nanoencapsulation therapies are actively being searched as an alternative for DA replacement. However, overcoming the low yield of encapsulation and/or poor biodistribution/bioavailability of DA is still a current challenge. Herein, we report the synthesis of a family of neuromelanin bioinspired polymeric nanoparticles. Our system is based on the encapsulation of DA within nanoparticles through its reversible coordination complexation to iron metal nodes polymerized with a bis-imidazol ligand. Our methodology, in addition to being simple and inexpensive, results in DA loading efficiencies of up to 60%. In vitro, DA nanoscale coordination polymers (DA-NCPs) exhibited lower toxicity, degradation kinetics, and enhanced uptake by BE(2)-M17 DArgic cells compared to free DA. Direct infusion of the particles in the ventricle of rats in vivo showed a rapid distribution within the brain of healthy rats, leading to an increase in striatal DA levels. More importantly, after 4 days of nasal administrations with DA-NCPs equivalent to 200 μg of the free drug per day, the number and duration of apomorphine-induced rotations was significantly lower from that in either vehicle or DA-treated rats performed for comparison purposes. Overall, this study demonstrates the advantages of using nanostructured DA for DA-replacement therapy. © 2021 American Chemical Society.
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Coordination polymers nanoparticles for bioimaging
Suárez-García S., Solórzano R., Novio F., Alibés R., Busqué F., Ruiz-Molina D. Coordination Chemistry Reviews; 432 (213716) 2021. 10.1016/j.ccr.2020.213716. IF: 22.315
Early diagnosis of patient diseases is subjected to the appropriate use of bioimaging techniques. For this reason, the development of contrast agents that improve and enhance the response of current clinical imaging practices is a pressing concern. Non-invasive bioimaging techniques most often need specific probes to follow and measure biological routes in living systems. These molecular imaging agents must exhibit: I) a remarkable contrast effect, i.e. a high signal-to-noise ratio under real physiological conditions, II) pronounced in vivo stability under the effect of numerous enzymes or proteases present in serum or targeted tissue equilibrated with a fast clearance from healthy organs and III) low cost and eco-friendly production. To overcome current drawbacks that hindrance the full development of the different bioimaging techniques, several groups are exploring nanoparticles as contrast agents. In this scenario, coordination polymer nanoparticles have emerged as a handy platform offering predesigned unique advantages thanks to their chemical flexibility, structural diversity and tailoring skills. Indeed, these systems reveal high metal cargos, low toxicity and multifunctional character by adequately selecting the combination of metal ions and ligands. Moreover, in a reminiscent way of organic polymeric nanoparticles, coordination polymer nanoparticles have also demonstrated its ability to encapsulate therapeutic-active molecules, thus combining diagnostic and therapeutic functionalities, the so-called Theranostic nanomedicine. For all these reasons, the use of this family of nanoparticles as imaging contrast agents has attracted broad interest over the last years with numerous examples being reported. Herein, we review main accomplishments in the area grouped according to the used technology, including magnetic resonance imaging, computed tomography, optical imaging, radioimaging or photoacoustic imaging. © 2020 Elsevier B.V.
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Hybrid Metal-Phenol Nanoparticles with Polydopamine-like Coating for PET/SPECT/CT Imaging
SuÃirez-GarcÃ-A S., Esposito T.V.F., Neufeld-Peters J., Bergamo M., Yang H., Saatchi K., Schaffer P., HÃfeli U.O., Ruiz-Molina D., RodrÃ-Guez-RodrÃ-Guez C., Novio F. ACS Applied Materials and Interfaces; 13 (9): 10705 - 10718. 2021. 10.1021/acsami.0c20612. IF: 9.229
The validation of metal-phenolic nanoparticles (MPNs) in preclinical imaging studies represents a growing field of interest due to their versatility in forming predesigned structures with unique properties. Before MPNs can be used in medicine, their pharmacokinetics must be optimized so that accumulation in nontargeted organs is prevented and toxicity is minimized. Here, we report the fabrication of MPNs made of a coordination polymer core that combines In(III), Cu(II), and a mixture of the imidazole 1,4-bis(imidazole-1-ylmethyl)-benzene and the catechol 3,4-dihydroxycinnamic acid ligands. Furthermore, a phenolic-based coating was used as an anchoring platform to attach poly(ethylene glycol) (PEG). The resulting MPNs, with effective hydrodynamic diameters of around 120 nm, could be further derivatized with surface-embedded molecules, such as folic acid, to facilitate in vivo targeting and multifunctionality. The prepared MPNs were evaluated for in vitro plasma stability, cytotoxicity, and cell internalization and found to be biocompatible under physiological conditions. First, biomedical evaluations were then performed by intrinsically incorporating trace amounts of the radioactive metals 111In or 64Cu during the MPN synthesis directly into their polymeric matrix. The resulting particles, which had identical physicochemical properties to their nonradioactive counterparts, were used to perform in vivo single-photon emission computed tomography (SPECT) and positron emission tomography (PET) in tumor-bearing mice. The ability to incorporate multiple metals and radiometals into MPNs illustrates the diverse range of functional nanoparticles that can be prepared with this approach and broadens the scope of these nanoconstructs as multimodal preclinical imaging agents. ©
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Photoactivable ruthenium-based coordination polymer nanoparticles for light-induced chemotherapy
Zhang J., Ramu V., Zhou X.-Q., Frias C., Ruiz-Molina D., Bonnet S., Roscini C., Novio F. Nanomaterials; 11 (11, 3089) 2021. 10.3390/nano11113089. IF: 5.076
Green light photoactive Ru-based coordination polymer nanoparticles (CPNs), with chemical formula [[Ru(biqbpy)]1.5 (bis)](PF6)3 (biqbpy = 6,6′-bis[N-(isoquinolyl)-1-amino]-2,2′-bipyridine; bis = bis(imidazol-1-yl)-hexane), were obtained through polymerization of the trans-[Ru(biqbpy) (dmso)Cl]Cl complex (Complex 1) and bis bridging ligands. The as-synthesized CPNs (50 ± 12 nm di-ameter) showed high colloidal and chemical stability in physiological solutions. The axial bis(imidazole) ligands coordinated to the ruthenium center were photosubstituted by water upon light irradiation in aqueous medium to generate the aqueous substituted and active ruthenium complexes. The UV-Vis spectral variations observed for the suspension upon irradiation corroborated the photoactivation of the CPNs, while High Performance Liquid Chromatography (HPLC) of irradiated particles in physiological media allowed for the first time precisely quantifying the amount of photoreleased complex from the polymeric material. In vitro studies with A431 and A549 cancer cell lines revealed an 11-fold increased uptake for the nanoparticles compared to the monomeric complex [Ru(biqbpy)(N-methylimidazole)2 ](PF6)2 (Complex 2). After irradiation (520 nm, 39.3 J/cm2), the CPNs yielded up to a two-fold increase in cytotoxicity compared to the same CPNs kept in the dark, indicating a selective effect by light irradiation. Meanwhile, the absence of1 O2 production from both nanostructured and monomeric prodrugs concluded that light-induced cell death is not caused by a photodynamic effect but rather by photoactivated chemotherapy. © 2021 by the authors. Licensee MDPI, Basel, Switzerland.
2020
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Luminescent silicon-based nanocarrier for drug delivery in colorectal cancer cells
Marcelo G.A., Montpeyo D., Novio F., Ruiz-Molina D., Lorenzo J., Oliveira E. Dyes and Pigments; 181 (108393) 2020. 10.1016/j.dyepig.2020.108393. IF: 4.613
Nanocarriers sensitive to exogenous or endogenous stimuli emerged as an attractive alternative to target drug delivery, with inorganic silica mesoporous nanoparticles (MNs) playing a core role in the development of a new generation of non-toxic and tuneable nanocarriers. A sensitive nanovector (NANO1) comprising luminescent silicon quantum dots (SiQDs) and functionalized with MNs was synthesised and loaded with doxorubicin (DOX). NANO1 nanoparticles have a size of 74 ± 10 nm and DOX loading percentages of ca. 43%. As a control sample, a similar nanocarrier (NANO2), without SiQDs, was also synthesised and loaded with DOX. Release profile studies, in PBS, revealed the strong NANO1@DOX pH-dependant behaviour, with a pH 5.0 favouring the release of DOX to percentages of ca. 70%. Cytotoxicity assessments of both free and DOX-loaded nanocarriers were evaluated in human cell lines of colon, revealing both free drug and drug-loaded nanoparticles to be concentration-dependent. © 2020 Elsevier Ltd
2018
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Dual T1/ T2 Nanoscale Coordination Polymers as Novel Contrast Agents for MRI: A Preclinical Study for Brain Tumor
Suárez-García S., Arias-Ramos N., Frias C., Candiota A.P., Arús C., Lorenzo J., Ruiz-Molina D., Novio F. ACS Applied Materials and Interfaces; 10 (45): 38819 - 38832. 2018. 10.1021/acsami.8b15594. IF: 8.097
In the last years, extensive attention has been paid on designing and developing functional imaging contrast agents for providing accurate noninvasive evaluation of pathology in vivo. However, the issue of false-positives or ambiguous imaging and the lack of a robust strategy for simultaneous dual-mode imaging remain to be fully addressed. One effective strategy for improving it is to rationally design magnetic resonance imaging (MRI) contrast agents (CAs) with intrinsic T1/T2 dual-mode imaging features. In this work, the development and characterization of one-pot synthesized nanostructured coordination polymers (NCPs) which exhibit dual mode T1/T2 MRI contrast behavior is described. The resulting material comprises the combination of different paramagnetic ions (Fe3+, Gd3+, Mn2+) with selected organic ligands able to induce the polymerization process and nanostructure stabilization. Among them, the Fe-based NCPs showed the best features in terms of colloidal stability, low toxicity, and dual T1/T2 MRI contrast performance overcoming the main drawbacks of reported CAs. The dual-mode CA capability was evaluated by different means: in vitro phantoms, ex vivo and in vivo MRI, using a preclinical model of murine glioblastoma. Interestingly, the in vivo MRI of Fe-NCPs show T1 and T2 high contrast potential, allowing simultaneous recording of positive and negative contrast images in a very short period of time while being safer for the mouse. Moreover, the biodistribution assays reveals the persistence of the nanoparticles in the tumor and subsequent gradual clearance denoting their biodegradability. After a comparative study with commercial CAs, the results suggest these nanoplatforms as promising candidates for the development of dual-mode MRI CAs with clear advantages. © 2018 American Chemical Society.
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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. IF: 3.173
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
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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. IF: 6.735
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.
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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. IF: 5.160
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
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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. IF: 1.184
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
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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.