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1.
ACS Appl Mater Interfaces ; 14(15): 17531-17538, 2022 04 20.
Artigo em Inglês | MEDLINE | ID: mdl-35380791

RESUMO

Volatile methylsiloxanes (VMSs) are common silicone degradation byproducts that cause serious concern for the contamination of sensitive electronics and optics, among others. With the goal of fast, online detection of VMS, we herein highlight the mesoporous MIL-101(Cr) MOF as a promising mass sensing layer for integration with a quartz crystal microbalance (QCM), using an in-house modified gravimetric adsorption system capable of achieving extremely low concentrations of siloxane D4 (down to 0.04 ppm), targeting applications for monitoring in indoor spaces and spacecraft. Our developed MIL-101(Cr)@QCM sensor achieves near-perfect reversibility with no hysteresis alongside excellent repeatability over cycling and fast response/recovery times under 1 min. We attribute this capability to optimum host/guest interactions as uncovered through molecular simulations.

2.
Chem Asian J ; 17(13): e202200129, 2022 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-35472103

RESUMO

The realization of metal-organic framework (MOF) layers onto solid surfaces is a prerequisite for their integration into devices. This work reports the direct growth of Fe3+ /benzene di-carboxylate MOFs onto functionalized silicon surfaces, compatible with a wide range of MOF synthesis conditions. The co-nucleation and growth of different crystalline phases are evidenced, whose coverage depends on the surface chemistry and/or the solution composition. Three structural phases - the cubic MIL-101(Fe), a hexagonal phase with a structure close to MOF-235 and a MIL-53(Fe) with a monoclinic symmetry - are identified through characteristic crystal shapes and their structural parameters inferred from X-Ray Diffraction. In addition to the oriented growth of 3D crystallites, the formation of two-dimensional MIL-101 nano-crystallites or thin layers/islands exhibiting extended monocrystalline domains with (111) texture is also demonstrated through high-resolution atomic force microscopy. Post-synthesis treatments reveal a weak adhesion of the hexagonal phase, indicating a different surface anchoring.

3.
Dalton Trans ; 50(43): 15914-15923, 2021 Nov 09.
Artigo em Inglês | MEDLINE | ID: mdl-34723313

RESUMO

A highly performing proton conducting composite was prepared through the impregnation of EMIMCl ionic liquid in the mesoporous MIL-101(Cr)-SO3H MOF. The resulting EMIMCl@MIL-101(Cr)-SO3H composite displays high thermal and chemical stability, alongside retention of a high amount of EMIMCl even at temperatures as high as 500 K, as well as under moisture conditions. Remarkably, this composite exhibits outstanding proton conductivity not only at the anhydrous state (σ473 K = 1.5 × 10-3 S cm-S) but also under humidity (σ(343 K/60%-80%RH) ≥ 0.10 S cm-1) conditions. This makes EMIMCl@MIL-101(Cr)-SO3H a unique candidate to act as a solid state proton conductor for PEMFC applications under versatile conditions.

4.
Angew Chem Int Ed Engl ; 59(26): 10353-10358, 2020 Jun 22.
Artigo em Inglês | MEDLINE | ID: mdl-32187798

RESUMO

An innovative strategy is proposed to synthesize single-crystal nanowires (NWs) of the Al3+ dicarboxylate MIL-69(Al) MOF by using graphene oxide nanoscrolls as structure-directing agents. MIL-69(Al) NWs with an average diameter of 70±20 nm and lengths up to 2 µm were found to preferentially grow along the [001] crystallographic direction. Advanced characterization methods (electron diffraction, TEM, STEM-HAADF, SEM, XPS) and molecular modeling revealed the mechanism of formation of MIL-69(Al) NWs involving size-confinement and templating effects. The formation of MIL-69(Al) seeds and the self-scroll of GO sheets followed by the anisotropic growth of MIL-69(Al) crystals are mediated by specific GO sheets/MOF interactions. This study delivers an unprecedented approach to control the design of 1D MOF nanostructures and superstructures.

5.
Angew Chem Int Ed Engl ; 57(49): 16141-16146, 2018 12 03.
Artigo em Inglês | MEDLINE | ID: mdl-30307095

RESUMO

Microperoxidase-8, a small, peroxidase-type enzyme was immobilized into nanoparticles of the mesoporous and ultra-stable metal-organic framework (MOF) MIL-101(Cr). The immobilized enzyme fully retained its catalytic activity and exhibited enhanced resistance to acidic conditions. The biocatalyst was reusable and showed a long-term stability. By exploiting the properties of the MOF's framework, we demonstrated, for the first time, that the MOF matrix could act in synergy with the enzyme (Microperoxidase-8) and enhance selectivity the oxidation reaction of dyes. The oxidation rate of the harmful negatively charged dye (methyl orange) was significantly increased after enzyme immobilization, probably as a result of the pre-concentration of the methyl orange reactant owing to a charge matching between this dye and the MOF.


Assuntos
Corantes/química , Estruturas Metalorgânicas/química , Peroxidases/química , Corantes/metabolismo , Enzimas Imobilizadas/química , Enzimas Imobilizadas/metabolismo , Concentração de Íons de Hidrogênio , Estruturas Metalorgânicas/metabolismo , Modelos Moleculares , Estrutura Molecular , Nanopartículas/química , Nanopartículas/metabolismo , Tamanho da Partícula , Peroxidases/metabolismo , Porosidade , Propriedades de Superfície
6.
ACS Appl Mater Interfaces ; 10(16): 13886-13894, 2018 Apr 25.
Artigo em Inglês | MEDLINE | ID: mdl-29613759

RESUMO

The removal of low concentrations of acetic acid from indoor air at museums poses serious preservation problems that the current adsorbents cannot easily address owing to their poor affinity for acetic acid and/or their low adsorption selectivity versus water. In this context, a series of topical water-stable metal-organic frameworks (MOFs) with different pore sizes, topologies, hydrophobic characters, and functional groups was explored through a joint experimental-computational exploration. We demonstrate how a subtle combination of sufficient hydrophobicity and optimized host-guest interactions allows one to overcome the challenge of capturing traces of this very polar volatile organic compound in the presence of humidity. The optimal capture of acetic acid was accomplished with MOFs that do not show polar groups in the inorganic node or have lipophilic but polar (e.g., perfluoro) groups functionalized to the organic linkers, that is, the best candidates from the list of explored MOFs are MIL-140B and UiO-66-2CF3. These two MOFs present the appropriate pore size to favor a high degree of confinement, together with organic spacers that allow an enhancement of the van der Waals interactions with the acetic acid. We establish in this work that MOFs can be a viable solution to this highly challenging problem in cultural heritage protection, which is a new field of application for this type of hybrid materials.

7.
Nat Commun ; 9(1): 1660, 2018 04 25.
Artigo em Inglês | MEDLINE | ID: mdl-29695794

RESUMO

Porous titanium oxide materials are attractive for energy-related applications. However, many suffer from poor stability and crystallinity. Here we present a robust nanoporous metal-organic framework (MOF), comprising a Ti12O15 oxocluster and a tetracarboxylate ligand, achieved through a scalable synthesis. This material undergoes an unusual irreversible thermally induced phase transformation that generates a highly crystalline porous product with an infinite inorganic moiety of a very high condensation degree. Preliminary photophysical experiments indicate that the product after phase transformation exhibits photoconductive behavior, highlighting the impact of inorganic unit dimensionality on the alteration of physical properties. Introduction of a conductive polymer into its pores leads to a significant increase of the charge separation lifetime under irradiation. Additionally, the inorganic unit of this Ti-MOF can be easily modified via doping with other metal elements. The combined advantages of this compound make it a promising functional scaffold for practical applications.

8.
Chemistry ; 24(31): 7949-7956, 2018 Jun 04.
Artigo em Inglês | MEDLINE | ID: mdl-29573349

RESUMO

To gain insight into the influence of metal-organic framework (MOF) fillers and polymers on membrane performance, eight different composites were studied by combining four MOFs and two polymers. MOF materials (NH2 -MIL-53(Al), MIL-69(Al), MIL-96(Al) and ZIF-94) with various chemical functionalities, topologies, and dimensionalities of porosity were employed as fillers, and two typical polymers with different permeability-selectivity properties (6FDA-DAM and Pebax) were selected as matrices. The best-performing MOF-polymer composites were prepared by loading 25 wt % of MIL-96(Al) as filler, which improved the permeability and selectivity of 6FDA-DAM to 32 and 10 %, while for Pebax they were enhanced to 25 and 18 %, respectively. The observed differences in membrane performance in the separation of CO2 from N2 are explained on the basis of gas solubility, diffusivity properties, and compatibility between the filler and polymer phases.

9.
Chem Soc Rev ; 46(11): 3431-3452, 2017 Jun 06.
Artigo em Inglês | MEDLINE | ID: mdl-28537319

RESUMO

Owing to their promise in photocatalysis and optoelectronics, titanium based metal-organic frameworks (MOFs) are one of the most appealing classes of MOFs reported to date. Nevertheless, Ti-MOFs are still very scarce because of their challenging synthesis associated with a poor degree of control of their chemistry and crystallization. This review aims at giving an overview of the recent progress in this field focusing on the most relevant existing titanium coordination compounds as well as their promising photoredox properties. Not only Ti-MOFs but also Ti-oxo-clusters will be discussed and particular interest will be dedicated to highlight the different successful synthetic strategies allowing to overcome the still "unpredictable" reactivity of titanium ions, particularly to afford crystalline porous coordination polymers.

10.
ChemSusChem ; 10(7): 1419-1426, 2017 04 10.
Artigo em Inglês | MEDLINE | ID: mdl-28160428

RESUMO

The energy-storage capacities of a series of water-stable porous metal-organic frameworks, based on high-valence metal cations (Al3+ , Fe3+ , Cr3+ , Ti4+ , Zr4+ ) and polycarboxylate linkers, were evaluated under the typical conditions of seasonal energy-storage devices. The results showed that the microporous hydrophilic Al-dicarboxylate MIL-160(Al) exhibited one of the best performances. To assess the properties of this material for space-heating applications on a laboratory pilot scale with an open reactor, a new synthetic route involving safer, greener conditions was developed. This led to the production of MIL-160(Al) on a 400 g scale, before the material was shaped into pellets through a wet-granulation method. The material exhibited a very high energy-storage capacity for a physical-sorption material (343 Wh kg-1 ), which is in full agreement with the predicted value.


Assuntos
Alumínio/química , Temperatura Alta , Interações Hidrofóbicas e Hidrofílicas , Compostos Organometálicos/química , Compostos Organometálicos/síntese química , Técnicas de Química Sintética , Modelos Moleculares , Conformação Molecular
11.
ACS Appl Mater Interfaces ; 8(40): 27311-27321, 2016 Oct 12.
Artigo em Inglês | MEDLINE | ID: mdl-27600279

RESUMO

A study integrating advanced experimental and modeling tools was undertaken to characterize the microstructural and interfacial properties of mixed matrix membranes (MMMs) composed of the zeolitic imidazolate framework ZIF-8 nanoparticles (NPs) and two polymers of intrinsic microporosity (PIM-1 and PIM-EA-TB). Analysis probed both the initial ZIF-8/PIM-1 colloidal suspensions and the final hybrid membranes. By combination of dynamic light scattering (DLS) and transmission electron microscopy (TEM) analytical and imaging techniques with small-angle X-ray scattering (SAXS), the colloidal suspensions were shown to consist mainly of two distinct kinds of particles, namely, polymer aggregates of about 200 nm in diameter and densely packed ZIF-8-NP aggregates of a few 100 nm in diameter with a 3 nm thick polymer top-layer. Such aggregates are likely to impart the granular texture of ZIF-8/PIMs MMMs as shown by SEM-XEDS analysis. At the molecular scale, modeling studies showed that the surface coverage of ZIF-8 NPs by both polymers appears not to be optimal with the presence of microvoids at the interfaces that indicates only a moderate compatibility between the polymer and ZIF-8. This study shows that the microstructure of MMMs results from a complex interplay between the ZIF-8/PIM compatibility, solvent, surface chemistry of the ZIF-8 NPs, and the physicochemical properties of the polymers such as molecular structure and rigidity.

12.
ACS Appl Mater Interfaces ; 8(31): 20012-22, 2016 Aug 10.
Artigo em Inglês | MEDLINE | ID: mdl-27447023

RESUMO

Laccase in combination with 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) as a mediator is a well-known bioelectrocatalyst for the 4-electron oxygen reduction reactions (ORR). The present work deals with the first exploitation of mesoporous iron(III) trimesate-based metal organic frameworks (MOF) MIL-100(Fe) (MIL stands for materials from Institut Lavoisier) as a new and efficient immobilization matrix of laccase for the building up of biocathodes for ORR. First, the immobilization of ABTS in the pores of the MOF was studied by combining micro-Raman spectroscopy, X-ray powder diffraction (XRPD), and N2 porosimetry. The ABTS-MIL-100(Fe)-based modified electrode presents excellent properties in terms of charge transfer kinetics and ionic conductivity as well as a very stable and reproducible electrochemical response, showing that MIL-100(Fe) provides a suitable and stabilizing microenvironment for electroactive ABTS molecules. In a second step, laccase was further immobilized on the MIL-100(Fe)-ABTS matrix. The Lac-ABTS-MIL-100(Fe)-CIE bioelectrode presents a high electrocatalytic current density of oxygen reduction and a reproducible electrochemical response characterized by a high stability over a long period of time (3 weeks). These results constitute a significant advance in the field of laccase-based bioelectrocatalysts for ORR. According to our work, it appears that the high catalytic efficiency of Lac-ABTS-MIL-100(Fe) for ORR may result from a synergy of chemical and catalytic properties of MIL-100(Fe) and laccase.

13.
Chemistry ; 22(19): 6564-74, 2016 May 04.
Artigo em Inglês | MEDLINE | ID: mdl-27080557

RESUMO

The chemically and structurally highly stable polyoxometalate (POM) single-molecule magnet (SMM) [(FeW9 O34 )2 Fe4 (H2 O)2 ](10-) (Fe6 W18 ) has been incorporated by direct or post-synthetic approaches into a biopolymer gelatin (Gel) matrix and two crystalline metal-organic frameworks (MOFs), including one diamagnetic (UiO-67) and one magnetic (MIL-101(Cr)). Integrity of the POM in the Fe6 W18 @Gel, Fe6 W18 @UiO-67 and Fe6 W18 @MIL-101(Cr) composites was confirmed by a set of complementary techniques. Magnetic studies indicate that the POMs are magnetically well isolated. Remarkably, in Fe6 W18 @Gel, the SMM properties of the embedded molecules are close to those of the crystals, with clear quantum tunneling steps in the hysteresis loops. For the Fe6 W18 @UiO-67 composite, the molecules retain their SMM properties, the energy barrier being slightly reduced in comparison to the crystalline material and the molecules exhibiting a tunneling rate of magnetization significantly faster than for Fe6 W18 @Gel. When Fe6 W18 is introduced into MIL-101(Cr), the width of the hysteresis loops is drastically reduced and the quantum tunneling steps are smeared out because of the magnetic interactions between the antiferromagnetic matrix and the SMM guest molecules.

14.
J Mater Chem B ; 3(46): 8983-8992, 2015 Dec 14.
Artigo em Inglês | MEDLINE | ID: mdl-32263029

RESUMO

Nanocomposites combining the mesoporous iron(iii) trimesate MIL-100(Fe) (MIL: Matériaux Institut Lavoisier) and platinum nanoparticles (Pt-NPs) have been used as immobilization matrices of glucose oxidase (GOx). Due to the physico-chemical properties of Pt-NPs (electroactivity) and MIL-100(Fe) (high specific surface area and pore volume, biocompatibility), the resulting GOx-MIL-100(Fe)-PtNP bioelectrode exhibits excellent electrocatalytic performances for glucose detection. This novel glucose biosensor presents a high sensitivity of 71 mA M-1 cm-2 under optimum conditions and a low limit of detection of 5 µM with low response time (<5 s). In contrast, substitution of iron by chromium or aluminum in MIL-100 leads to a much lower sensitivity and higher response time values, suggesting that the iron centres of MIL-100(Fe) may be involved in a synergistic effect which indeed enhances the catalytic oxidation of glucose and biosensor activity. Thus, this work extends the scope of MOF nanoparticles with engineered cores and surface to the field of highly sensitive, durable glucose biosensors.

15.
Chem Commun (Camb) ; 49(71): 7773-5, 2013 Sep 14.
Artigo em Inglês | MEDLINE | ID: mdl-23687655

RESUMO

A 1D-microporous 3D calcium tetracarboxylate MOF has been solvothermally prepared and its structure solved from single crystal data. It exhibits coordinatively unsaturated Ca(2+) Lewis acid sites able to trap and deliver nitric oxide at a biological level.


Assuntos
Cálcio/química , Óxido Nítrico/metabolismo , Materiais Biocompatíveis/química , Materiais Biocompatíveis/metabolismo , Ácidos de Lewis/química , Porosidade
16.
Nanotechnology ; 21(18): 185605, 2010 May 07.
Artigo em Inglês | MEDLINE | ID: mdl-20388968

RESUMO

Gold-alginate bionanocomposite films were prepared by impregnation of alginate films with HAuCl(4) followed by reduction with glucose. The mannuronate over guluronate ratio (M/G) of the polymer as well as the initial polymer concentration were shown to influence the film thickness, the amount of trapped Au(3 + ) ions, and the volume fraction of Au(0) nanoparticles but not the size of these colloids (about 4 nm). The homogeneity of the gold colloid dispersion within the alginate gels was studied by transmission electron microscopy (TEM) and confirmed by simulation of the surface plasmon resonance (SPR) spectra using the Maxwell-Garnett model. The calculated spectra also provided fruitful information about the gold colloid/alginate interface. Overall, the whole process is controlled by the balance between the M/G ratio, defining the polymer affinity for Au(III) species, and the solution viscosity, controlling the diffusion phenomena.

17.
J Am Chem Soc ; 132(13): 4653-68, 2010 Apr 07.
Artigo em Inglês | MEDLINE | ID: mdl-20232862

RESUMO

This work shows that the combination of first-principles calculations and (51)V NMR experiments is a powerful tool to elucidate the location of surface hydroxyl groups and to precisely describe the hydrogen bond network in the complex decavanadate cluster Cs(4)[H(2)V(10)O(28)].4H(2)O, enhancing the strength of NMR crystallography. The detailed characterization of H-bond networks for these kinds of inorganic compounds is of primary importance and should benefit from the DFT-NMR predictions by considering explicitly the periodic boundary conditions. The determination of the Cs(4)[H(2)V(10)O(28)].4H(2)O structure by single-crystal X-ray diffraction was not sufficiently accurate to provide the location of protons. From available diffraction data, five different protonated model structures have been built and optimized using DFT-based methods. The possible interconversion of two decavanadate isomers through a proton exchange is evaluated by calculating the energy barrier and recording variable-temperature (1)H MAS NMR spectra. First-principles calculations of (51)V NMR parameters clearly indicate that these parameters are very sensitive to the local intermolecular hydrogen-bonding interactions. Considering the DFT error limits, the fairly good agreement between calculated and experimental NMR parameters arising from the statistical modeling of the data allows the unambiguous assignment of the five (51)V NMR signals and, thus, the location of OH surface ligands in the decavanadate cluster. In particular, first-principles calculations accurately reproduce the (51)V quadrupolar parameters. These results are fully consistent with (51)V 3QMAS NMR spectra recorded with and without (1)H decoupling. Finally, correlations are established between local octahedral VO(6) deformations and (51)V NMR parameters (C(q) and Deltadelta), which will be useful for the characterization of a wide range of chemical species containing vanadium(V).

18.
J Phys Chem B ; 112(40): 12596-605, 2008 Oct 09.
Artigo em Inglês | MEDLINE | ID: mdl-18795771

RESUMO

The influence of polyoxovanadate clusters ([H(2)V(10)O(28)](4-)) on the thermo-reversible gelation of porcine skin gelatin solution (type A, M w approximately 40 000 g.mol (-1), pH = 3.4 << isoelectric point (IEP) approximately 8) has been investigated as a function of temperature and vanadate concentration by combining rheology and microcalorimetry. This work shows that the rheological properties of the system depend on electrostatic interactions between [H(2)V(10)O(28)](4-) and positively charged gelatin chains. In a first stage, we describe the renaturation of the gelatin triple helices in the presence of decavanadate clusters. We reveal that, when gelatin chains are in coil conformation (30 degrees C < T < 50 degrees C), the inorganic clusters act as physical cross-linkers that govern the visco-elastic properties of the mixture with an exponential dependence of the (G', G'') modulus with the vanadate concentration. Below 30 degrees C, we show that gelatin triple helix nucleation is slightly favored by the presence of vanadate, but above a helix concentration of 0.012 g.cm (-3), G' is fully governed by the helix concentration. During the melting process, we reveal the non-fully reversible behavior of the vanadate/gelatin rheological properties and the stabilization of gelatin triple helices due to vanadate species until 50 degrees C. This non-reversible character has also been observed in the same experimental conditions with collagen/vanadate solutions. This is the first time that such a stabilization of triple helices has been reported in the case of gelatin hydrogels chemically cross-linked or not. We propose to analyze these results by considering that triple helix aggregates should persist because of decavanadate bridging, that the nucleation of an extended triple helix network may induce a strong modification of the vanadate cross-linker distribution in the system, or both, thus promoting the formation of thermally stable vanadate/gelatin micro-gels in the dangling end of the triple helices.


Assuntos
Gelatina/química , Animais , Colágeno/química , Transição de Fase , Desnaturação Proteica , Reologia , Suínos , Vanadatos/química
19.
Soft Matter ; 4(4): 735-738, 2008 Mar 20.
Artigo em Inglês | MEDLINE | ID: mdl-32907176

RESUMO

The first example of complex coacervation between a biopolymer and polyoxometalate clusters is identified in the gelatin-decavanadate system.

20.
Inorg Chem ; 43(6): 2021-30, 2004 Mar 22.
Artigo em Inglês | MEDLINE | ID: mdl-15018525

RESUMO

The reaction of vanadate(V) with a series of dipeptides (Val-Gln, Ala-Gln, Gly-Gln, Gly-Glu, and Ala-Gly) was investigated by UV-visible spectroscopy and multinuclear ((51)V, (14)N, (13)C) NMR spectroscopy in solution. It was possible to evaluate the formation constants of the corresponding complexes for which a molecular structure was proposed. Complex formation is favored by the presence of a functionalized or a sterically demanding side chain. The Val-Gln dipeptide which combines both properties exhibits one of the highest formation constant reported so far for dipeptides.


Assuntos
Dipeptídeos/química , Vanadatos/química , Concentração de Íons de Hidrogênio , Espectroscopia de Ressonância Magnética , Estrutura Molecular , Soluções/química , Espectrofotometria Ultravioleta
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