Degradation and Erosion of Metal-Organic Frameworks: Comparative Study of a NanoMIL-100 Drug Delivery System.

To make a drug work better, the active substance can be incorporated into a vehicle for optimal protection and control of the drug delivery time and space. For making the drug carrier, the porous metal-organic framework (MOF) can offer high drug-loading capacity and various designs for effective drug delivery performance, biocompatibility, and biodegradability. Nevertheless, its degradation process is complex and not easily predictable, and the toxicity concern related to the MOF degradation products remains a challenge for their clinical translation. Here, we describe an in-depth molecular and nanoscale degradation mechanism of aluminum- and iron-based nanoMIL-100 materials exposed to phosphate-buffered saline. Using a combination of analytical tools, including X-ray photoelectron spectroscopy, nuclear magnetic resonance spectroscopy, small-angle X-ray scattering, and electron microscopy, we demonstrate qualitatively and quantitatively the formation of a new coordination bond between metal(III) and phosphate, trimesate release, and correlation between these two processes. Moreover, the extent of material erosion, i.e., bulk or surface erosion, was examined from the transformation of nanoparticles' surface, morphology, and interaction with water. Similar analyses show the impact of drug loading and surface coating on nanoMIL-100 degradation and drug release as a function of the metal-ligand binding strength. Our results indicate how the chemistry of nanoMIL-100(Al) and nanoMIL-100(Fe) drug carriers affects their degradation behaviors in a simulated physiological medium. This difference in behavior between the two nanoMIL-100s enables us to better correlate the nanoscale and atomic-scale mechanisms of the observed phenomena, thus validating the presented multiscale approach.

3D multiscale analysis of the hierarchical porosity in Coscinodiscus sp. diatoms using a combination of tomographic techniques.

A full 3D analysis of the hierarchical porosity in Coscinodiscus sp. diatom structures was carried out by using a multiscale approach that combines three advanced volumetric imaging techniques with resolutions and fields of view covering all the porous characteristics of such complex architectures: electron tomography, "slice and view" approach that uses a dual-beam microscope (FIB-SEM), and array tomography consisting of serial imaging of ultrathin specimen sections. This multiscale approach allowed the whole porosity network to be quantified and provided an unprecedented structural insight into these natural nanostructured materials with internal organization ranging from micrometer to nanometer. The analysed species is made of several nested layers with different pore sizes, shapes and connectivities and characterized by the presence of interconnected pores structured in various ways. The first evidence of the presence of a nanometric porosity made of ellipsoidal pores in the siliceous diatom frustules is also provided.

Impact of surface diffusion on transport through porous materials.

The peak parking method was applied to evaluate the surface diffusivity Ds of polystyrenes dissolved in a THF/heptane mixture and transported through porous silica materials with various morphologies. With this method, the overall effective diffusivity D is measured experimentally with coarse-grained models like Maxwell equation allowing one to infer the particle diffusivity Dpz. Such particle diffusivity has two main contributions: in-pore diffusivity Dp and surface diffusivity Ds. The diffusion within the pores is determined experimentally using either non-adsorbing conditions or calculated from particle porosity, particle tortuosity, and hydrodynamic hindrance. The surface diffusion coefficient Ds is usually determined using models considering parallel diffusion in the pores and at the surface but this assumption is rather crude. In this paper, to address this problem, another approach is proposed using the Brownian motion of molecules in the pore space. These two approaches lead to similar equations relating the effective diffusion coefficient D, the in-pore diffusion Dp and surface diffusion Ds. The surface diffusion is analyzed as a function of the surface affinity of the probes considered here (polystyrenes of different molecular weights/lengths). Such surface affinity depends both on the probe chain length and surface chemistry of the host solid (the latter being characterized here through the silanol surface density). For short chain lengths, a non-monotonic change in the surface diffusion with affinity (i.e. retention factor) is observed in some cases. Yet, generally, as expected, surface diffusion decreases upon increasing the surface affinity. In contrast to short chain lengths, the longest chain lengths are less sensitive to the silanol surface density.

Mercury cyclic porosimetry: Measuring pore-size distributions corrected for both pore-space accessivity and contact-angle hysteresis.

We propose a set of simple formulae for interpreting "mercury cyclic porosimetry" measurements where multiple intrusion-extrusion cycles are carried out. By employing two parameters α∈[0,1] and κ∈[0,1], our theory quantitatively breaks down any hysteresis observed in cyclic porosimetry data into contributions due to connectivity effects and contact-angle hysteresis, respectively. In particular, the parameter α, called "pore-space accessivity", characterizes any serial connectivity between different-size pores. It has long been recognized that the standard method for determining the pore-size distribution (PSD) from mercury intrusion data based on the capillary bundle assumption overestimates the fraction of smaller pores; that corresponds to the α→1 limit of our model. In contrast, for materials with α<1, our theory predicts a broadened PSD shifted toward larger radii, thus representing a simple way of rectifying PSDs for connectivity effects. The proposed model also establishes mercury cyclic porosimetry as a standard experimental procedure for measuring α, which can then be used in continuum models of porous media where connectivity effects play a significant role, such as in multiphase flow.

Bridging scales in disordered porous media by mapping molecular dynamics onto intermittent Brownian motion.

Owing to their complex morphology and surface, disordered nanoporous media possess a rich diffusion landscape leading to specific transport phenomena. The unique diffusion mechanisms in such solids stem from restricted pore relocation and ill-defined surface boundaries. While diffusion fundamentals in simple geometries are well-established, fluids in complex materials challenge existing frameworks. Here, we invoke the intermittent surface/pore diffusion formalism to map molecular dynamics onto random walk in disordered media. Our hierarchical strategy allows bridging microscopic/mesoscopic dynamics with parameters obtained from simple laws. The residence and relocation times - tA, tB - are shown to derive from pore size d and temperature-rescaled surface interaction ε/kBT. tA obeys a transition state theory with a barrier ~ε/kBT and a prefactor ~10-12 s corrected for pore diameter d. tB scales with d which is rationalized through a cutoff in the relocation first passage distribution. This approach provides a formalism to predict any fluid diffusion in complex media using parameters available to simple experiments.

Green earth pigments dispersions: Water dynamics at the interfaces.

HYPOTHESIS: The objective is to elucidate the multiscale dynamics of water within natural mixtures of minerals, green earth pigments that are mainly composed of phyllosilicates containing large amount of iron. In particular, the interaction of water with the different kinds of surfaces has to be probed. One issue is to examine the influence of surface type, basal or edge, on the dispersion quality. EXPERIMENT: The study was carried out using 1H variable field NMR relaxometry on various green earth pigment dispersions and concentrations. To analyse the data, a new analytical model was developed for natural phyllosilicates containing large amount of paramagnetic centres. FINDING: The proposed theoretical framework is able to fit the experimental data for various samples using few parameters. It allows to determining water diffusion and residence times in complex phyllosilicate dispersions. Furthermore, it makes it possible to differentiate the contribution of the basal and edge surfaces and their respective surface area in interaction with water. Moreover, NMR relaxation profile reveals to be highly sensitive to the structural aspect of the phyllosilicates and to the accessibility of water to iron, hence allowing to discriminate clearly between two very similar phyllosilicates (glauconite and celadonite) that are difficult to distinguish by standard structural methods.

Green Earth pigments aqueous dispersions: NMR relaxation rates dataset.

The data presented here are related to the research paper entitled "Green Earth pigments dispersions: water dynamics at the interfaces". The nuclear magnetic resonance (NMR) relaxometry data are provided for various aqueous Green Earth (GE) pigments dispersions with volume fraction spanning approximately from 0.1 to 0.5. For two of them (Cyprus GE and Bohemian GE), the NMR relaxation profiles from 10 kHz to 30 MHz (1H frequency) is given for several temperatures spanning from 293 to 318K. In addition, the X-ray diffraction pattern is provided for France GE (Kremer pigments) for the identification of the main mineral component. The nitrogen gas isotherms are provided for Cyprus GE and Bohemian GE.

Insights into the Formation Mechanism of CdSe Nanoplatelets Using in Situ X-ray Scattering.

Two-dimensional ultrathin CdSe nanoplatelets have attracted a large interest due to their optical properties but their formation mechanism is not well understood. Several different mechanisms have been proposed: confined growth in a surfactant mesophase acting as a template, anisotropic ripening of small seeds into 2D nanoplatelets, or continuous anisotropic growth of a limited number of nuclei. However, quantitative in situ data that could validate or disprove these formation scenarios are lacking. We use synchrotron-based small-angle and wide-angle X-ray scattering to probe the formation mechanism of CdSe nanoplatelets synthesized using a heating-up method. We prove the absence of a molecular mesophase in the reactive medium at the onset of nanoplatelet formation ruling out a templating effect. We also show that our data are inconsistent with the anisotropic ripening of small seeds whereas the evolution of the SAXS patterns during the reaction is consistent with the continuous lateral growth of nanoplatelets fed by reactive monomers. Finally, we show that when the final temperature of the synthesis is lowered, nanoplatelets with larger lateral dimensions form. We reveal that they bend in solution during their growth to yield nanoscrolls.

Aggregation of Plate-like Colloids Induced by Charged Polymer Chains: Organization at the Nanometer Scale Tuned by Polymer Charge Density.

We study the aggregation of charged plate-like colloids, Na-montmorillonite clays, in the presence of ionenes, oppositely charged polymer chains. The choice of the charged polymer allows tuning its linear charge density to match/mismatch the average charge separation on the clay surfaces. We assess the nanoscale structure of the aggregates formed by small-angle X-ray and neutron scattering. The nanoscale features of the formed clay aggregates are dominated by the presence of a stacking peak, giving clear evidence for the formation of clay tactoids, that is, a face-to-face aggregation geometry of the clay platelets. The chain charge density of ionenes influences not only the stacking repeat distance within the clay tactoids but also the extent of stacking and abundance of the tactoids. We may distinguish two regimes as a function of clay and ionene polymer charge densities (ρc and ρp, respectively). The first regime applies to ρp > ρc and ρp ≈ ρc, that is, for highly and "matching" charged chains. Under these conditions, the intercalated chains lie in a flat conformation within the tactoids, irrespective of the ionic strength (within the range studied, i.e., up to 0.05 M NaBr). For weakly charged chains, ρp < ρc, undulation of the ionene chains within the tactoid is seen. The degree of undulation increases with ionic strength due to the decreasing persistence length of the ionene chains. The extent of stacking (5-10 platelets per tactoid) is a general feature of all the systems, and its origin remains unknown. The system corresponding to the closest match in charge separations on the clay surface and on the polymer chain (ρp ≈ ρc) features the highest abundance of tactoids. This coincides with the highest macroscopic density as deduced from simple visual inspection of sediment volumes. This leads to the open question regarding the link between the density at the nanoscale and the macroscopic density and sedimentation behavior of the aggregate.

Mesoscale structure, mechanics, and transport properties of source rocks' organic pore networks.

Organic matter is responsible for the generation of hydrocarbons during the thermal maturation of source rock formation. This geochemical process engenders a network of organic hosted pores that governs the flow of hydrocarbons from the organic matter to fractures created during the stimulation of production wells. Therefore, it can be reasonably assumed that predictions of potentially recoverable confined hydrocarbons depend on the geometry of this pore network. Here, we analyze mesoscale structures of three organic porous networks at different thermal maturities. We use electron tomography with subnanometric resolution to characterize their morphology and topology. Our 3D reconstructions confirm the formation of nanopores and reveal increasingly tortuous and connected pore networks in the process of thermal maturation. We then turn the binarized reconstructions into lattice models including information from atomistic simulations to derive mechanical and confined fluid transport properties. Specifically, we highlight the influence of adsorbed fluids on the elastic response. The resulting elastic energy concentrations are localized at the vicinity of macropores at low maturity whereas these concentrations present more homogeneous distributions at higher thermal maturities, due to pores' topology. The lattice models finally allow us to capture the effect of sorption on diffusion mechanisms with a sole input of network geometry. Eventually, we corroborate the dominant impact of diffusion occurring within the connected nanopores, which constitute the limiting factor of confined hydrocarbon transport in source rocks.

Flocculation of Clay Colloids Induced by Model Polyelectrolytes: Effects of Relative Charge Density and Size.

Flocculation and its tuning are of utmost importance in the optimization of several industrial protocols in areas such as purification of waste water and civil engineering. Herein, we studied the polyelectrolyte-induced flocculation of clay colloids on a model system consisting of purified clay colloids of well-defined size fractions and ionene polyelectrolytes presenting regular and tunable chain charge density. To characterize ionene-induced clay flocculation, we turned to the combination of light absorbance (turbidity) and ζ-potential measurements, as well as adsorption isotherms. Our model system allowed us to identify the exact ratio of positive and negative charges in clay-ionene mixtures, the (c+/c-) ratio. For all samples studied, the onset of efficient flocculation occurred consistently at c+/c- ratios significantly below 1, which indicated the formation of highly ionene-deficient aggregates. At the same time, the ζ-potential measurements indicated an apparent zero charge on such aggregates. Thus, the ζ-potential values could not provide the stoichiometry inside the clay-ionene aggregates. The early onset of flocculation in clay-ionene mixtures is reminiscent of the behavior of multivalent salts and contrasts that of monovalent salts, for which a large excess amount of ions is necessary to achieve flocculation. Clear differences in the flocculation behavior are visible as a function of the ionene charge density, which governs the conformation of the ionene chains on the clay surface.

New approach for understanding experimental NMR relaxivity properties of magnetic nanoparticles: focus on cobalt ferrite.

Relaxivities r1 and r2 of cobalt ferrite magnetic nanoparticles (MNPs) have been investigated in the aim of improving the models of NMR relaxation induced by magnetic nanoparticles. On one hand a large set of relaxivity data has been collected for cobalt ferrite MNP dispersions. On the other hand the relaxivity has been calculated for dispersions of cobalt ferrite MNPs with size ranging from 5 to 13 nm, without using any fitting procedure. The model is based on the magnetic dipolar interaction between the magnetic moments of the MNPs and the 1H nuclei. It takes into account both the longitudinal and transversal contributions of the magnetic moments of MNPs leading to three contributions in the relaxation equations. The comparison of the experimental and theoretical data shows a good agreement of the NMR profiles as well as the temperature dependence.

Mesoscale texture of cement hydrates.

Strength and other mechanical properties of cement and concrete rely upon the formation of calcium-silicate-hydrates (C-S-H) during cement hydration. Controlling structure and properties of the C-S-H phase is a challenge, due to the complexity of this hydration product and of the mechanisms that drive its precipitation from the ionic solution upon dissolution of cement grains in water. Departing from traditional models mostly focused on length scales above the micrometer, recent research addressed the molecular structure of C-S-H. However, small-angle neutron scattering, electron-microscopy imaging, and nanoindentation experiments suggest that its mesoscale organization, extending over hundreds of nanometers, may be more important. Here we unveil the C-S-H mesoscale texture, a crucial step to connect the fundamental scales to the macroscale of engineering properties. We use simulations that combine information of the nanoscale building units of C-S-H and their effective interactions, obtained from atomistic simulations and experiments, into a statistical physics framework for aggregating nanoparticles. We compute small-angle scattering intensities, pore size distributions, specific surface area, local densities, indentation modulus, and hardness of the material, providing quantitative understanding of different experimental investigations. Our results provide insight into how the heterogeneities developed during the early stages of hydration persist in the structure of C-S-H and impact the mechanical performance of the hardened cement paste. Unraveling such links in cement hydrates can be groundbreaking and controlling them can be the key to smarter mix designs of cementitious materials.

Noninvasive Experimental Evidence of the Linear Pore Size Dependence of Water Diffusion in Nanoconfinement.

We show that nuclear magnetic relaxation experiments at variable magnetic fields (NMRD) provide noninvasive means for probing the spatial dependence of liquid diffusion close to solid interfaces. These experiments performed on samples of cylindrical and spherical nanopore geometries demonstrate that the average diffusion coefficient parallel to the interface is proportional to the pore radii in different dynamics regimes. A master curve method allows extraction of gradients of diffusion coefficients in proximity of the pore surfaces, indicative of the efficiency of coupling between liquid layers. Due to their selectivity in frequency, NMRD experiments are able to differentiate the different water dynamical events induced by heterogeneous surfaces or composed dynamical processes. This analysis relevant in physical and biological confinements highlights the interplay between the molecular and continuous description of fluid dynamics near interfaces.

Confinement, Desolvation, And Electrosorption Effects on the Diffusion of Ions in Nanoporous Carbon Electrodes.

Supercapacitors are electrochemical devices which store energy by ion adsorption on the surface of a porous carbon. They are characterized by high power delivery. The use of nanoporous carbon to increase their energy density should not hinder their fast charging. However, the mechanisms for ion transport inside electrified nanopores remain largely unknown. Here we show that the diffusion is characterized by a hierarchy of time scales arising from ion confinement, solvation, and electrosorption effects. By combining electrochemistry experiments with molecular dynamics simulations, we determine the in-pore conductivities and diffusion coefficients and their variations with the applied potential. We show that the diffusion of the ions is slower by 1 order of magnitude compared to the bulk electrolyte. The desolvation of the ions occurs on much faster time scales than electrosorption.

Modeling the arrangement of particles in natural swelling-clay porous media using three-dimensional packing of elliptic disks.

Swelling clay minerals play a key role in the control of water and pollutant migration in natural media such as soils. Moreover, swelling clay particles' orientational properties in porous media have significant implications for the directional dependence of fluid transfer. Herein we investigate the ability to mimic the organization of particles in natural swelling-clay porous media using a three-dimensional sequential particle deposition procedure [D. Coelho, J.-F. Thovert, and P. M. Adler, Phys. Rev. E 55, 1959 (1997)]. The algorithm considered is first used to simulate disk packings. Porosities of disk packings fall onto a single master curve when plotted against the orientational scalar order parameter value. This relation is used to validate the algorithm used in comparison with existing ones. The ellipticity degree of the particles is shown to have a negligible effect on the packing porosity for ratios ℓ(a)/ℓ(b) less than 1.5, whereas a significant increase in porosity is obtained for higher values. The effect of the distribution of the geometrical parameters (size, aspect ratio, and ellipticity degree) of particles on the final packing properties is also investigated. Finally, the algorithm is used to simulate particle packings for three size fractions of natural swelling-clay mineral powders. Calculated data regarding the distribution of the geometrical parameters and orientation of particles in porous media are successfully compared with experimental data obtained for the same samples. The results indicate that the obtained virtual porous media can be considered representative of natural samples and can be used to extract properties difficult to obtain experimentally, such as the anisotropic features of pore and solid phases in a system.

Interplay of anisotropy in shape and interactions in charged platelet suspensions.

Motivated by the intriguing phase behavior of charged colloidal platelets, we investigate the structure and dynamics of charged repulsive disks by means of Monte Carlo simulations. The electrostatic interactions are taken into account through an effective two-body potential, obtained within the nonlinear Poisson-Boltzmann formalism, which has the form of anisotropic screened Coulomb potential. Recently, we showed that the original intrinsic anisotropy of the electrostatic potential in competition with excluded volume effects leads to a rich phase behavior that not only includes various liquid-crystalline phases but also predicts the existence of novel structures composed of alternating nematic-antinematic sheets. Here, we examine the structural and dynamical signatures of each of the observed structures for both translational and rotational degrees of freedom. Finally, we discuss the influence of effective charge value and our results in relation to experimental findings on charged platelet suspensions.

Imaging Drosophila brain by combining cryo-soft X-ray microscopy of thick vitreous sections and cryo-electron microscopy of ultrathin vitreous sections.

Cryo-soft X-ray microscopy is an emerging imaging tool complementary to cryo-electron microscopy, allowing to image frozen hydrated specimens ten to hundred times thicker, but at lower resolution. We describe how the method, so far restricted to isolated small cells or cell monolayers, can be extended to large cells and tissue. We image the synapses of the Kenyon cells in frozen hydrated Drosophila brains combining cryo-soft X-ray microscopy of thick vitreous sections, and cryo-electron microscopy of ultrathin vitreous sections. We show how to obtain frozen hydrated sections of thicknesses ranging from 40 nm up to 2.5 µm, by tuning the sectioning speed of the cryo-microtome. A fluorescent stereo-microscope mounted on the cryo-microtome allowed us to target the regions of interest after GFP-labeling of synapses. Thick cryo-sections were imaged by cryo-soft X-ray microscopy at a resolution better than 25 nm, while ultrathin cryo-sections of the same regions were explored in parallel at the nanometre level of resolution by cryo-electron microscopy.

On phase behavior and dynamical signatures of charged colloidal platelets.

Charged platelet suspensions, such as swelling clays, disc-like mineral crystallites or exfoliated nanosheets are ubiquitous in nature. Their phase behaviours are nevertheless still poorly understood: while some clay suspensions form arrested states at low densities, others exhibit an equilibrium isotropic-nematic transition at moderate densities. These observations raise fundamental questions about the influence of electrostatic interactions on the isotropic-nematic transition and the organisation of charged platelets. We investigate the competition between anisotropic excluded-volume and repulsive electrostatic interactions in suspensions of charged colloidal discs, by means of Monte-Carlo simulations and characterization of the dynamics of the structures. We show that the original intrinsic anisotropy of the electrostatic potential between charged platelets not only rationalizes generic features of the complex phase diagram of charged colloidal platelets such as Gibbsite and Beidellite clays, but also predicts the existence of novel structures. Furthermore, we find evidences of a strong slowing down of the dynamics upon increasing density.

High-resolution cellular MRI: gadolinium and iron oxide nanoparticles for in-depth dual-cell imaging of engineered tissue constructs.

Recent advances in cell therapy and tissue engineering opened new windows for regenerative medicine, but still necessitate innovative noninvasive imaging technologies. We demonstrate that high-resolution magnetic resonance imaging (MRI) allows combining cellular-scale resolution with the ability to detect two cell types simultaneously at any tissue depth. Two contrast agents, based on iron oxide and gadolinium oxide rigid nanoplatforms, were used to "tattoo" endothelial cells and stem cells, respectively, with no impact on cell functions, including their capacity for differentiation. The labeled cells' contrast properties were optimized for simultaneous MRI detection: endothelial cells and stem cells seeded together in a polysaccharide-based scaffold material for tissue engineering appeared respectively in black and white and could be tracked, at the cellular level, both in vitro and in vivo. In addition, endothelial cells labeled with iron oxide nanoparticles could be remotely manipulated by applying a magnetic field, allowing the creation of vessel substitutes with in-depth detection of individual cellular components.