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Near-surface rheology and hydrodynamic boundary condition of semi-dilute polymer solutions
Laboratoire Indysoft - Gabriel Guyard Alexandre Vilquin Nicolas Sanson Frederic Restagno Joshua D. Mcgraw
HAL - 1 - https://hal.archives-ouvertes.fr/hal-03029154 - 2020
Understanding confined flows of complex fluids requires simultaneous access to the mechanical behaviour of the liquid and the boundary condition at the interfaces. Here, we use evanescent wave microscopy to investigate near-surface flows of semi-dilute, unentangled polyacrylamide solutions. By using both neutral and anionic polymers, we show that monomer charge plays a key role in confined polymer dynamics. For solutions in contact with glass, the neutral polymers display chain-sized adsorbed layers, while a shear-rate-dependent apparent slip length is observed for anionic polymer solutions. The slip lengths measured at all concentrations collapse onto a master curve when scaled using a simple two-layer depletion model with non-Newtonian viscosity. A transition from an apparent slip boundary condition to a chain-sized adsorption layer is moreover highlighted by screening the charge with additional salt in the anionic polymer solutions. We anticipate that our study will be a starting point for more complex studies relating the polymer dynamics at interfaces to their chemical and physical composition.
Interface-Sensitive Raman Microspectroscopy of Water via Confinement with a Multimodal Miniature Surface Forces Apparatus
Laboratoire INDYSOFT - Hilton B. de Aguiar, Joshua D. McGraw, and Stephen H. Donaldson Jr.
Langmuir - 35(48) 15543–15551 - doi.org/10.1021/acs.langmuir.9b01889 - 2020
Modern interfacial science is increasingly multidisciplinary. Unique insight into interfacial interactions requires new multimodal techniques for interrogating surfaces with simultaneous complementary physical and chemical measurements. Here, we describe the design and testing of a microscope that incorporates a miniature surface forces apparatus (μSFA) in sphere vs flat geometry for force–distance measurements, while simultaneously acquiring Raman spectra of the confined zone. The simple optical setup isolates independent optical paths for (i) the illumination and imaging of Newton’s rings and (ii) Raman scattering excitation and efficient signal collection. We benchmark the methodology by examining Teflon thin films in asymmetric (Teflon–water–glass) and symmetric (Teflon–water–Teflon) configurations. Water is observed near the Teflon–glass interface with nanometer-scale sensitivity in both the distance and Raman signals. We perform chemically resolved, label-free imaging of confined contact regions between Teflon and glass surfaces immersed in water. Remarkably, we estimate that the combined approach enables vibrational spectroscopy with single water monolayer sensitivity within minutes. Altogether, the Raman-μSFA allows exploration of molecular confinement between surfaces with chemical selectivity and correlation with interaction forces.
Multimodal Miniature Surface Forces Apparatus (μSFA) for Interfacial Science Measurements
Laboratoire INDYSOFT - Kai Kristiansen, Stephen H. Donaldson Jr., Zachariah J. Berkson, Jeffrey Scott, Rongxin Su, Xavier Banquy, Dong Woog Lee, Hilton B. de Aguiar, Joshua D. McGraw, George D. Degen, and Jacob N. Israelachvili
Langmuir - 35(48) 15500–15514 - doi.org/10.1021/acs.langmuir.9b01808 - 2020
Advances in the research of intermolecular and surface interactions result from the development of new and improved measurement techniques and combinations of existing techniques. Here, we present a new miniature version of the surface forces apparatus—the μSFA—that has been designed for ease of use and multimodal capabilities with the retention of the capabilities of other SFA models including accurate measurements of the surface separation distance and physical characterization of dynamic and static physical forces (i.e., normal, shear, and friction) and interactions (e.g., van der Waals, electrostatic, hydrophobic, steric, and biospecific). The small physical size of the μSFA, compared to previous SFA models, makes it portable and suitable for integration into commercially available optical and fluorescence light microscopes, as demonstrated here. The large optical path entry and exit ports make it ideal for concurrent force measurements and spectroscopy studies. Examples of the use of the μSFA in combination with surface plasmon resonance (SPR) and Raman spectroscopy measurements are presented. Because of the short working distance constraints associated with Raman spectroscopy, an interferometric technique was developed and applied to calculate the intersurface separation distance based on Newton’s rings. The introduction of the μSFA will mark a transition in SFA usage from primarily physical characterization to concurrent physical characterization with in situ chemical and biological characterization to study interfacial phenomena, including (but not limited to) molecular adsorption, fluid flow dynamics, the determination of surface species and morphology, and (bio)molecular binding kinetics.
Time dependence of advection-diffusion coupling for nanoparticle ensembles
Laboratoire INDYSOFT - Alexandre Vilquin Vincent Bertin Pierre Soulard Gabriel Guyard Elie Raphaël Frederic Restagno Thomas Salez Joshua Mcgraw
HAL - 1 - https://hal.archives-ouvertes.fr/hal-02896493 - 2020
Particle transport in fluids at micro-and nano-scales is important in many domains. As compared to the quiescent case, the time evolution of particle dispersion is enhanced by coupling: i) advection along the flow; and ii) diffusion along the associated velocity gradients. While there is a well-known, long-time limit for this advection-diffusion enhancement, understanding the short-time limit and corresponding crossover between these two asymptotic limits is less mature. We use evanescent-wave video microscopy for its spatio-temporal resolution. Specifically, we observe a near-surface zone of where the velocity gradients, and thus dispersion, are the largest within a simple microfluidic channel. Supported by a theoretical model and simulations based on overdamped Langevin dynamics, our experiments reveal the crossover of this so-called Taylor dispersion from short to long time scales. Studying a range of particle size, viscosity and applied pressure, we show that the initial spatial distribution of particles can strongly modify observed master curves for short-time dispersion and its crossover into the long-time regime.
Influence of outer-layer finite-size effects on the dewetting dynamics of a thin polymer film embedded in an immiscible matrix
Laboratoire INDYSOFT - M. S. Chebil,a J. D. McGraw, T. Salez, C. Sollogoub and G. Miquelard-Garnier
Soft Matter - 14 6256-6263 - doi.org/10.1039/C8SM00592C - 2020
In capillary-driven fluid dynamics, simple departures from equilibrium offer the chance to quantitatively model the resulting relaxations. These dynamics in turn provide insight on both practical and fundamental aspects of thin-film hydrodynamics. In this work, we describe a model trilayer dewetting experiment elucidating the effect of solid, no-slip confining boundaries on the bursting of a liquid film in a viscous environment. This experiment was inspired by an industrial polymer processing technique, multilayer coextrusion, in which thousands of alternating layers are stacked atop one another. When pushed to the nanoscale limit, the individual layers are found to break up on time scales shorter than the processing time. To gain insight on this dynamic problem, we here directly observe the growth rate of holes in the middle layer of the trilayer films described above, wherein the distance between the inner film and solid boundary can be orders of magnitude larger than its thickness. Under otherwise identical experimental conditions, thinner films break up faster than thicker ones. This observation is found to agree with a scaling model that balances capillary driving power and viscous dissipation with a no-slip boundary condition at the solid substrate/viscous environment boundary. In particular, even for the thinnest middle-layers, no finite-size effect related to the middle film is needed to explain the data. The dynamics of hole growth is captured by a single master curve over four orders of magnitude in the dimensionless hole radius and time, and is found to agree well with predictions including analytical expressions for the dissipation.
Adsorption-induced slip inhibition for polymer melts on ideal substrates
Laboratoire INDYSOFT - Mark Ilton, Thomas Salez, Paul D. Fowler, Marco Rivetti, Mohammed Aly, Michael Benzaquen, Joshua D. McGraw, Elie Raphaël, Kari Dalnoki-Veress & Oliver Bäumchen
Nat Commun - 9 1172 - doi.org/10.1039/C8SM00592C - 2020
Hydrodynamic slip, the motion of a liquid along a solid surface, represents a fundamental phenomenon in fluid dynamics that governs liquid transport at small scales. For polymeric liquids, de Gennes predicted that the Navier boundary condition together with polymer reptation implies extraordinarily large interfacial slip for entangled polymer melts on ideal surfaces; this Navier-de Gennes model was confirmed using dewetting experiments on ultra-smooth, low-energy substrates. Here, we use capillary leveling—surface tension driven flow of films with initially non-uniform thickness—of polymeric films on these same substrates. Measurement of the slip length from a robust one parameter fit to a lubrication model is achieved. We show that at the low shear rates involved in leveling experiments as compared to dewetting ones, the employed substrates can no longer be considered ideal. The data is instead consistent with a model that includes physical adsorption of polymer chains at the solid/liquid interface.
Self-Similar Relaxation of Confined Microfluidic Droplets
Laboratoire INDYSOFT - Margaux Kerdraon1, Joshua D. McGraw1, Benjamin Dollet2, and Marie-Caroline Jullien
Phys. Rev. Lett. - 123 024501 - doi.org/10.1103/PhysRevLett.123.024501 - 2020
We report an experimental study concerning the capillary relaxation of a confined liquid droplet in a microscopic channel with a rectangular cross section. The confinement leads to a droplet that is extended along the direction normal to the cross section. These droplets, found in numerous microfluidic applications, are pinched into a peanutlike shape thanks to a localized, reversible deformation of the channel. Once the channel deformation is released, the droplet relaxes back to a pluglike shape. During this relaxation, the liquid contained in the central pocket drains towards the extremities of the droplet. Modeling such viscocapillary droplet relaxation requires considering the problem as 3D due to confinement. This 3D consideration yields a scaling model incorporating dominant dissipation within the droplet menisci. As such, the self-similar droplet dynamics is fully captured.
Natural Abundance Oxygen-17 Solid-State NMR of Metal Organic Frameworks Enhanced by Dynamic Nuclear Polarization
Laboratoire Institut des Matériaux Poreux de Paris - Carnevale D, Mouchaham G, Wang S, Baudin M, Serre C, Bodenhausen G, Abergel D
ChemRxiv - - DOI: 10.26434/chemrxiv.12477449.v1 - 2020
The 17O resonances of Zirconium-oxo clusters that can be found in porous Zr carboxylate metal-organic frameworks (MOFs) have been investigated by magic-angle spinning (MAS) NMR spectroscopy enhanced by dynamic nuclear polarization (DNP). High-resolution 17O spectra at 0.037 % natural abundance could be obtained in 48 hours, thanks to DNP enhancement of the 1H polarization by factors e(1H) = Swith/Swithout = 28, followed by 1H®17O cross-polarization, allowing a saving in experimental time by a factor of ca. 800. The distinct 17O sites from the oxo-clusters can be resolved at 18.8 T. Their assignment is supported by density functional theory (DFT) calculations of chemical shifts and quadrupolar parameters.
One‐step versatile room temperature synthesis of metal(IV) carboxylate MOFs
Laboratoire Institut des Matériaux Poreux de Paris - Shan Dai, Farid Nouar, Sanjun Zhang, Antoine Tissot, and Christian Serre
Angew. Chem. Int. Ed - - : https://doi.org/10.1002/anie.202014184 - 2020
This manuscript has been accepted after peer review and appears as an Accepted Article online prior to editing, proofing, and formal publication of the final Version of Record (VoR). This work is currently citable by using the Digital Object Identifier (DOI) given below. The VoR will be published online in Early View as soon as possible and may be different to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published to ensure accuracy of information. The authors are responsible for the content of this Accepted Article.
Principal Component Analysis (PCA) for Powder Diffraction Data: Towards Unblinded Applications
Laboratoire Institut des Matériaux Poreux de Paris - Shan Dai, Farid Nouar, Sanjun Zhang, Antoine Tissot, and Christian Serre
Angew. Chem. Int. Ed - - doi.org/10.1002/anie.202014184 - 2020
The development of room temperature green syntheses of robust MOFs is of great interest to meet the demand of the sustainable chemistry and is a pre‐requisite for the incorporation of functional but fragile compounds in water stable MOFs. However, only few ambient conditions routes to produce metal(IV) based MOFs have been reported and most of them suffer from a very low yield and/or multiple steps that preclude their use for most applications. We report here a new versatile one‐step synthesis of a series of highly porous M 6 oxoclusters based MOFs (M= Zr, Hf, Ce) at room temperature, including 8 or 12‐connected micro/mesoporous solids with different functionalized organic ligands. The resulting compounds show varying degrees of defectivity, particularly for 12‐connected phases, while maintaining the chemical stability of the parent MOFs. We propose first insights for the efficient MOF preparation based on In‐situ kinetics observations. Remarkably, the synthetic versatility not only allows an efficient room temperature synthesis with a high space‐time yield, but also gives possibility to tune the particle size, which therefore paves the way for their practical use.
Principal Component Analysis (PCA) for Powder Diffraction Data: Towards Unblinded Applications
Laboratoire Institut des Matériaux Poreux de Paris - Dmitry Chernyshov, Iurii Dovgaliuk, Vadim Dyadkin and Wouter van Beek
CRYSTALS - 10 7 - https://doi.org/10.3390/cryst10070581 - 2020
We analyze the application of Principal Component Analysis (PCA) for untangling the main contributions to changing diffracted intensities upon variation of site occupancy and lattice dimensions induced by external stimuli. The information content of the PCA output consists of certain functions of Bragg angles (loadings) and their evolution characteristics that depend on external variables like pressure or temperature (scores). The physical meaning of the PCA output is to date not well understood. Therefore, in this paper, the intensity contributions are first derived analytically, then compared with the PCA components for model data; finally PCA is applied for the real data on isothermal gas uptake by nanoporous framework γ –Mg(BH 4 ) 2 . We show that, in close agreement with previous analysis of modulation diffraction, the variation of intensity of Bragg lines and the displacements of their positions results in a series of PCA components. Every PCA extracted component may be a mixture of terms carrying information on the average structure, active sub-structure, and their cross-term. The rotational ambiguities, that are an inherently part of PCA extraction, are at the origin of the mixing. For the experimental case considered in the paper, the extraction of the physically meaningful loadings and scores can only be achieved with a rotational correction. Finally, practical recommendations for non-blind applications, i.e., what boundary conditions to apply for the the rotational correction, of PCA for diffraction data are given.
Non-Isothermal Kinetics of Kr Adsorption by Nanoporous γ-Mg(BH4)2 from in Situ Synchrotron Powder Diffraction
Laboratoire Institut des Matériaux Poreux de Paris - Iurii Dovgaliuk*, Vadim Dyadkin, Mathieu Vander Donckt, Yaroslav Filinchuk*, and Dmitry Chernyshov
ACS Publications - 12(6) 7710–7716 - https://doi.org/10.1021/acsami.9b19239 - 2020
Crystalline materials with pore dimensions comparable to the kinetic diameters of the guest molecules are attractive for their potential use in adsorption and separation applications. The nanoporous γ-Mg(BH4)2 features one-dimensional channels matching this criterion for Kr uptake, which has been probed using synchrotron powder diffraction at various pressures and temperatures. It results in two coexisting crystalline phases with the limiting composition Mg(BH4)2·0.66Kr expecting the highest Kr content (50.7 wt % in the crystalline phase) reported for porous materials. Quasi-equilibrium isobars built from Rietveld refinements of Kr site occupancies were rationalized with a noncooperative lattice gas model, yielding the values of the thermodynamic parameters. The latter were independently confirmed from Kr fluorescence. We have also parameterized the pronounced kinetic hysteresis with a modified mean-field model adopted for the Arrhenius kinetics.
Factors Determining Microporous Material Stability in Water: The Curious Case of SAPO-37
Laboratoire Institut des Matériaux Poreux de Paris - Georgios N. Kalantzopoulos, Fredrik Lundvall, Knut Thorshaug, Anna Lind, Ponniah Vajeeston, Iurii Dovgaliuk, Bjørnar Arstad, David S. Wragg, and Helmer Fjellvåg
ACS Publications - 32(4) 1495–1505 - https://doi.org/10.1021/acs.chemmater.9b04510 - 2020
Silicoaluminophosphates (SAPOs) are a special class of zeolites that, due to their acidic and shape-selective properties, play a major role in ion exchange and separation processes and in crude oil cracking. SAPO-37 has the faujasite (FAU) topology same as zeolites X and Y, which are involved in more than 40% of the total crude oil conversion worldwide. A critical parameter that promotes detrimental structural transformations in SAPOs during real-life applications is the presence of humidity. In this study, we employ a multidisciplinary approach combining in situ synchrotron radiation powder X-ray diffraction (SR-PXRD), water adsorption, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and density functional theory (DFT) calculations to describe the mechanism and reveal the reasons why SAPO-37 collapses upon contact with humidity below 345 K. SR-PXRD revealed that the sodalite (SOD) cages (subunits of the FAU structure) have the strongest affinity to water during hydration below 345 K. Furthermore, below 345 K, the faujasite framework takes up an order of magnitude more water molecules than at temperatures above 345 K. DRIFTS confirmed the presence of Si–OH and P–OH surface structural defects that act as hydration centers, accelerating the loss of a long-range order. Finally, DFT calculations showed that the enthalpy of water adsorption in the sodalite cage and the faujasite supercage is −212 and −13 kJ/mol, respectively. The results presented in this work are highly topical for understanding the effect of water on the frameworks of the SAPO microporous catalysts family. The notorious instability of SAPO-37 is the result of the accumulative contribution of topological, physical, and chemical effects, leading to an array of rapidly evolving cascading effects. Our work shows how advancements in SR-PXRD methodology and hardware give new insight into highly dynamic features previously difficult to observe. In addition, this work introduces the conceptual insight that nonhomogeneous sorption of molecular species will induce dynamic features with dramatic consequences at both molecular and atomic levels. This is a highly impactful factor opening research paths for further work within catalysis, porous material design and chemistry, and sorption reactions and processes.
Metal-organic magnets with large coercivity and ordering temperatures up to 242°C
Laboratoire Institut des Matériaux Poreux de Paris - Panagiota Perlepe, Itziar Oyarzabal, Aaron Mailman4, Morgane Yquel, Mikhail
Science - 370(6516) 587-592 - DOI: 10.1126/science.abb3861 - 2020
Permanent magnets are generally produced from solid metals or alloys. Less dense compositions involving lighter elements tend to demagnetize well below room temperature or under modest applied external fields. Perlepe et al. now report that chemical reduction of a low-density chromium-pyrazine network produces a magnet that remains stable above 200°C and resists demagnetization with 7500-oersted coercivity at room temperature. The straightforward synthetic route to the material shows promise for broad exploration of potential applications.
Kinetic Barriers and Microscopic Mechanisms of Noble Gas Adsorption by Nanoporous γ‐Mg(BH4)2 Obtained by means of Sub‐Second X‐Ray Diffraction
Laboratoire Institut des Matériaux Poreux de Paris - Iurii Dovgaliuk Irena Senkovska Xiao Li Vadim Dyadkin Yaroslav Filinchuk Dmitry Chernyshov
Angew. Chem. Int. Ed - - https://doi.org/10.1002/anie.202015019 - 2020
Gas adsorption by porous frameworks sometimes result in structure “breathing”, “pores opening/closing”, “negative gas adsorption”, and other fascinating phenomena which can be revealed and explained with the use of in situ diffraction methods. The time‐dependent diffraction is able to address both kinetics of the guest uptake and structural response of the host framework, since the time evolution of the crystal structure bears the information on the mechanisms and kinetic barriers of guest adsorption. Using such advanced sub‐second in situ powder X‐ray diffraction, three various intracrystalline diffusion scenarios have been evaluated from the isothermal kinetics of Ar, Kr, and Xe adsorption by nanoporous γ‑Mg(BH4)2. These scenarios are dictated by two possible simultaneous transport mechanisms: diffusion through the intra‐ (i) and interchannel apertures (ii) of γ‐Mg(BH4)2 crystal structure. The contribution of i and ii changes depending on the kinetic diameter of the noble gas molecule and temperature regime. The lowest single activation barrier for the smallest Ar suggests equal diffusion of the atoms trough both pathways. Contrary, for the medium sized Kr we resolve the contributions of two parallel transport mechanisms, which tentatively can be attributed to the smaller barrier of the migration paths via the channel like pores and the higher barrier for the diffusion via narrow aperture between these channels. Remarkably, the largest Xe atoms diffuse only along 1D channels and show the highest single activation barrier. This work demonstrates a potential of sub‐second diffraction to access site‐specific kinetics of guest uptake in multi‐adsorption site frameworks.

A Robust Titanium Isophthalate Metal-Organic Framework for Visible-Light Photocatalytic CO2 Methanation
Laboratoire Institut des Matériaux Poreux de Paris - Sujing Wang Maria Cabrero-Antonino SergioNavalón Chen-chenCao AntoineTissot IuriiDovgaliuk JérômeMarrot CharlotteMartineau-Corcos LiangYu HaoWang WilliamShepard HermenegildoGarcía ChristianSerre1
Science - - https://doi.org/10.1016/j.chempr.2020.10.017 - 2020
Isophthalic acid (IPA) has been considered to build metal-organic frameworks (MOFs), owing to its facile availability, unique connection angle-mode, and a wide range of functional groups attached. Constructing titanium-IPA frameworks that possess photoresponse properties is an alluring characteristic with respect to the challenge of synthesizing new titanium-based MOFs (Ti-MOFs). Here, we report the first Ti-IPA MOF (MIP-208) that efficiently combines the use of preformed Ti8 oxoclusters and in situ acetylation of the 5-NH2-IPA linker. The mixed solid-solution linkers strategy was successfully applied, resulting in a series of multivariate MIP-208 structures with tunable chemical environments and sizable porosity. MIP-208 shows the best result among the pure MOF catalysts for the photocatalytic methanation of carbon dioxide. To improve the photocatalytic performance, ruthenium oxide nanoparticles were photo-deposited on MIP-208, forming a highly active and selective composite catalyst, MIP-208@RuOx, which features a notable visible-light response coupled with excellent stability and recycling ability.
A Mesoporous Zirconium-Isophthalate Multifunctional Platform
Laboratoire Institut des Matériaux Poreux de Paris - Ilich A.Ibarra, AídaGutiérrez-Alejandre, Ji Sun Lee, Jong-SanChang, ZhengLiu JérômeMarrot, WilliamShepard, GuillaumeMaurin, QiangXu, ChristianSerre
MATTER - - https://doi.org/10.1016/j.matt.2020.10.009 - 2020
Mesoporous materials suffer from poor crystallinity and hydrolytic stability, lack of chemical diversity, insufficient pore accessibility, complex synthesis, and toxicity issues. Here the association of Zr-oxo clusters and isophthalate via a homometallic-multicluster-dot strategy results in a robust mesoporous metal-organic framework, denoted as MIP-206 (MIP stands for materials of the Institute of Porous Materials of Paris), that overcomes the aforementioned limitations. MIP-206, with a combination of Zr6 and Zr12 oxo-cluster inorganic building units into a single structure, exhibits meso-channels of ca. 2.6 nm and displays excellent chemical stability. Owing to the abundant variety of functionalized isophthalic acid linkers, the chemical environment of MIP-206 can be tuned without hampering pore accessibility. MIP-206 loaded with palladium nanoparticles acts as an efficient and durable catalyst for the dehydrogenation of formic acid, outperforming benchmark mesoporous materials. This paves the way toward the utilization of MIP-206 as a mesoporous platform for a wide range of potential applications.
Formation of a Single Crystal Aluminum Based MOF Nanowire with Graphene Oxide Nanoscrolls as Structure& Directing Agents
Laboratoire Institut des Matériaux Poreux de Paris - Dr. Mégane Muschi Anusha Lalitha Dr. Saad Sene Dr. Damien Aureau Dr. Mathieu Fregnaux Dr. Imène Esteve Dr. Lucie Rivier Dr. Naseem Ramsahye
Angew. Chem. Int. Ed - 59(26) - https://doi.org/10.1002/anie.202000795 - 2020
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.
Tuning Cellular Biological Functions Through the Controlled Release of NO from a Porous Ti‐MOF
Laboratoire Institut des Matériaux Poreux de Paris - Rosana V. Pinto Dr. Sujing Wang Dr. Sergio R. Tavares Prof. João Pires Prof. Fernando Antunes Dr. Alexandre Vimont Prof. Guillaume Clet Prof. Marco Daturi
Angew. Chem. Int. Ed - 59(13) - https://doi.org/10.1002/anie.201913135 - 2020
Materials for the controlled release of nitric oxide (NO) are of interest for therapeutic applications. However, to date, many suffer from toxicity and stability issues, as well as poor performance. Herein, we propose a new NO adsorption/release mechanism through the formation of nitrites on the skeleton of a titanium‐based metal–organic framework (MOF) that we named MIP‐177, featuring a suitable set of properties for such an application: (i) high NO storage capacity (3 μmol mg−1solid), (ii) excellent biocompatibility at therapeutic relevant concentrations (no cytotoxicity at 90 μg mL−1 for wound healing) due to its high stability in biological media (<9 % degradation in 72 hours) and (iii) slow NO release in biological media (≈2 hours for 90 % release). The prospective application of MIP‐177 is demonstrated through NO‐driven control of mitochondrial respiration in cells and stimulation of cell migration, paving the way for the design of new NO delivery systems for wound healing therapy.
Encapsulation of Microperoxidase-8 in MIL-101(Cr)-X Nanoparticles: Influence of Metal–Organic Framework Functionalization on Enzymatic Immobilization and Catalytic Activity
Laboratoire Institut des Matériaux Poreux de Paris - Effrosyni Gkaniatsou, Rémy Ricoux*, Kalani Kariyawasam, Ingrid Stenger, Benhui Fan, Narjès Ayoub, Samanta Salas, Gilles Patriarche, Christian Serre, Jean-Pierre Mahy, Nathalie Steunou, and Clémence Sicard
ACS Publications - 3(4) 3233–3243 - https://doi.org/10.1021/acsanm.9b02464 - 2020
Microperoxidase 8 (MP8) was immobilized within MIL-101(Cr) bearing terephthalate linkers with functionalized groups (-NH2 and -SO3H). A synthesis protocol for MIL-101(Cr)-SO3H that avoids the use of toxic Cr(VI) and HF was developed. The electrostatic interactions between the MP8 molecules and the MOF matrices were found to be crucial for a successful immobilization. Raman spectroscopy revealed the dispersion of the immobilized MP8 molecules in MIL-101(Cr)-X matrices as monomers without aggregation. The presence of functional groups resulted in higher amounts of immobilized MP8 in comparison to the bare MIL-101(Cr). The catalytic activity of MP8@MIL-101(Cr)-NH2 per material mass was higher than that for MP8@MIL-101(Cr). The presence of free amino groups can thus improve the immobilization efficiency, leading to a higher amount of catalytically active species and improving the subsequent catalytic activity of the heterogeneous biocatalysts. MP8@MIL(Cr)-X also successfully catalyzed the selective oxidation of thioanisole derivatives into sulfoxides

638 publications.