Showing papers by "Daniel Maspoch published in 2016"
TL;DR: Nanoparticles@MOFs composites combine the tailorable porosity of MOFs with the versatile functionality of metal or metaloxide nanoparticles as mentioned in this paper, and have been shown to possess unique functional properties.
448 citations
TL;DR: A metal-organic framework (MOF) assembled from ZnII ions, 1,4-benzenedicarboxylate, and a hydrophobic carborane-based linker is reported, which can be switched between hydrophilic and superhydrophilic through a chemical treatment to remove some of the building blocks.
Abstract: Materials with surfaces that can be switched from high/superhydrophobicity to superhydrophilicity are useful for myriad applications. Herein, we report a metal-organic framework (MOF) assembled from ZnII ions, 1,4-benzenedicarboxylate, and a hydrophobic carborane-based linker. The MOF crystal-surface can be switched between hydrophobic and superhydrophilic through a chemical treatment to remove some of the building blocks.
70 citations
TL;DR: In this paper, the benefits of coupling spray-drying and continuous flow for continuous synthesis of metal-organic frameworks (MOFs) assembled from high-nuclearity secondary building units (SBUs) are reported.
Abstract: Metal–organic frameworks (MOFs) are among the most attractive porous materials currently available. However, one of the challenges precluding their industrial exploitation is the lack of methods for their continuous production. In this context, great advances have been enabled by recently discovered, novel continuous-fabrication methods such as mechanosynthesis, electrochemistry, continuous-flow synthesis and spray-drying. Herein we report the benefits of coupling two of these processes—spray-drying and continuous flow—for continuous synthesis of MOFs assembled from high-nuclearity secondary building units (SBUs). Using the resulting spray-drying continuous flow-assisted synthesis, we have prepared numerous members of diverse MOF families, including the UiO-66, Fe–BTC/MIL-100 and [Ni8(OH)4(H2O)2(L)6]n (where L = 1H-pyrazole-4-carboxylic acid) series. Interestingly, all of these MOFs were automatically obtained as compact microspherical superstructures (beads). We anticipate that our strategy could be easily employed for synthesizing and shaping multivariate (MTV) MOFs.
69 citations
TL;DR: In this paper, the authors report the use of a pillaring strategy for the design and synthesis of three novel amide-functionalized metal-organic frameworks (MOFs), TMUs-22/-23/-24, isoreticular to the recently reported imine functionalized TMU-6 and TMU21 MOFs.
Abstract: Here we report the use of a pillaring strategy for the design and synthesis of three novel amide-functionalized metal–organic frameworks (MOFs), TMUs-22/-23/-24, isoreticular to the recently reported imine-functionalized TMU-6 and TMU-21 MOFs. An extensive study of their CO2 sorption properties and selectivity for CO2 over N2, from single gas sorption isotherms to breakthrough measurements, revealed that not only the incorporation of amide groups but also their accessibility is crucial to obtain enhanced CO2 sorption and CO2/N2 selectivity. Therefore, the MOF with more accessible amide groups (TMU-24) shows a CO2/N2 selectivity value of ca. 10 (as revealed by breakthrough experiments), which is ca. 500% and 700% of the selectivity values observed for the other amide-containing (TMU-22 and TMU-23) and imine-containing (TMU-6 and TMU-21) MOFs.
67 citations
TL;DR: It is confirmed that liposome charge is critical to promote its accumulation in the brain infarct after MCAOt, and simvastatin encapsulation might be a promising strategy to ensure that the drug reaches the brain, while increasing its bioavailability and reducing possible side effects.
Abstract: The research leading to these results received funding from the European Union’s Seventh Framework Program (FP7/2007-2013) under grant agreements number
201024 and number 202213 (European Stroke Network). Neurovascular Research Laboratory takes part in the Spanish stroke research network INVICTUS (RD12/0014/0005). This study was partially funded by projects FIS 11/0176 on stroke biomarkers research and EC07/90195 on increasing safety and efficacy of simvastatin neuroprotection.
51 citations
TL;DR: A versatile methodology for engineering metallic Janus MOF particles based on desymmetrization at interfaces, whereby each MOF particle is partially coated with a desired metal is reported, which is expected to impart new functionalities to MOFs.
28 citations
TL;DR: It is proven experimentally and with numerical simulations that microfluidic technologies can undoubtedly fine-tune reaction times and reagents concentration profiles; factors that enable out-of-equilibrium crystal forms to be obtained.
Abstract: A methodology that can be efficiently used to synthesize, isolate, and study out-of-equilibrium crystal structures employing controlled and diffusion-limited microfluidic environments is demonstrated. Unlike studies conducted with conventional mixing procedures in a flask, it is proven experimentally and with numerical simulations that microfluidic technologies can undoubtedly fine-tune reaction times and reagents concentration profiles; factors that enable out-of-equilibrium crystal forms to be obtained.
20 citations
TL;DR: In this paper, the synthesis, X-ray crystallographic structure, and water uptake measurements of the first coordination polymer made of cyclodextrin and a transition metal ion (in this case, Cu2+) are shown.
Abstract: The synthesis, X-ray crystallographic structure, and water uptake measurements of the first coordination polymer made of a cyclodextrin and a transition metal ion (in this case, Cu2+) are shown. This coordination polymer is made by connecting paddle-wheel Cu2+ units through a γ-cyclodextrin functionalized with eight carboxylate groups, is stable in water, and shows selective water-induced reversible structural transformations.
18 citations
TL;DR: Through this transformation, which involves the cleavage and formation of different coordination bonds, two different Cu(II)-Zn(ii) and Cu(ii)-Ni(ii), paddlewheel units exhibiting a 1 : 1 metal ratio were created.
17 citations
TL;DR: In this article, hollow Pt or Pd nanoparticles were encapsulated into ZIF-8 and used as catalysts for the reduction of 4-nitrophenol and Eosin Y.
15 citations
TL;DR: A reversible breathing effect between the "open" and the "closed" structures of the MOF involves the cleavage and formation of several coordination bonds and a gate-opening effect at a relative humidity of 85% upon water adsorption.
TL;DR: In this article, a new macrocyclic linker 1,4,7,10tetraazacyclododecane-1,7-bis(4-acetamidobenzoic)-4,10-diacetic acid (H4L1) was synthesized and characterized.
Abstract: A new macrocyclic linker 1,4,7,10-tetraazacyclododecane-1,7-bis(4-acetamidobenzoic)-4,10-diacetic acid (H4L1) was synthesized and characterized. This linker was used to create two heterometallic coordination polymers following a two-step synthesis. This synthesis consisted of first combining this polyazamacrocyclic linker with Ni(II) or Mn(II) ions to obtain the corresponding metallomacrocyclic complexes showing non-coordinated carboxylic groups. In a second step, these metallated macrocycles were used as building units to construct two heterometallic Ni(II)–Zn(II) and Mn(II)–Zn(II) coordination polymers when combined with Zn(II) ions. In addition, a third Zn(II)–Zn(II) coordination polymer could also be synthesized by direct mixing of H4L1 with Zn(II) ions. Interestingly, the Mn(II)–Zn(II) coordination polymer exhibits a reversible type-I “crystal-to-amorphous transformation” upon water sorption/desorption.
TL;DR: The new coordination polymer (CP) is created by applying, for the first time, a stable Gd(III) chelate as building block in order to prevent any fortuitous release of free lanthanide( III) ion.
Abstract: Lanthanide-containing nanoscale particles have been widely explored for various biomedical purposes, however, they are often prone to metal leaching. Here we have created a new coordination polymer (CP) by applying, for the first time, a stable Gd(III) chelate as building block in order to prevent any fortuitous release of free lanthanide(III) ion. The use of the Gd-DOTA-4AmP complex as a design element in the CP allows not only for enhanced relaxometric properties (maximum r1 =16.4 mm(-1) s(-1) at 10 MHz), but also for a pH responsiveness (Δr1 =108 % between pH 4 and 6.5), beyond the values obtained for the low molecular weight Gd-DOTA-4AmP itself. The CP can be miniaturised to the nanoscale to form colloids that are stable in physiological saline solution and in cell culture media and does not show cytotoxicity.
TL;DR: The discovery of a less symmetric crystalline phase of Mn12 acetate, a triclinic phase, resulting from recrystallizing the original tetragonal phase reported by Lis in acetonitrile and toluene is reported.
Abstract: We report the discovery of a less symmetric crystalline phase of Mn12 acetate, a triclinic phase, resulting from recrystallizing the original tetragonal phase reported by Lis in acetonitrile and toluene. This new phase exhibits the same structure of Mn12 acetate clusters and the same positions of tunneling resonances on the magnetic field as the conventional tetragonal phase. However, the width of the zero-field resonance is at least 1 order of magnitude smaller—can be as low as 50 Oe—indicating very small inhomogeneous broadening due to dipolar and nuclear fields.
TL;DR: Nanoparticles@MOFs composites combine the tailorable porosity of MOFs with the versatile functionality of metal or metaloxide nanoparticles as mentioned in this paper, and have been shown to possess unique functional properties.
Abstract: Composites based on Metal-Organic Frameworks (MOFs) are an emerging class of porous materials that have been shown to possess unique functional properties. Nanoparticles@MOFs composites combine the tailorable porosity of MOFs with the versatile functionality of metal or metaloxide nanoparticles. A wide range of nanoparticles@MOFs have been synthesised and their performance characteristics assessed in molecular adsorption and separation, catalysis, sensing, optics, sequestration of pollutants, drug delivery, and renewable energy. This review covers the main research areas where nanoparticles@MOFs have been strategically applied and highlights the scientific challenges to be considered for their continuing development.
TL;DR: In this article, the authors reported characterization and magnetic studies of mixtures of micrometer-size ribbons of Mn12 acetate and particles of YBaCuO superconductor, pointing to the absence of the inhomogeneous dipolar broadening.
Abstract: We report characterization and magnetic studies of mixtures of micrometer-size ribbons of Mn12 acetate and micrometer-size particles of YBaCuO superconductor. Extremely narrow zero-field spin-tunneling resonance has been observed in the mixtures, pointing to the absence of the inhomogeneous dipolar broadening. It is attributed to the screening of the internal magnetic fields in the magnetic particles by Meissner currents flowing between superconducting grains surrounding the particles.