Synthetic routes toward MOF nanomorphologies.

As metal–organic frameworks (MOFs) are coming of age, their structural diversity, exceptional porosity and inherent functionality need to be transferred into useful applications. Fashioning MOFs into various shapes and at the same time controlling their size constitute an essential step toward MOF-based devices. Moreover, downsizing MOFs to the nanoscale triggers a whole new set of properties distinguishing nanoMOFs from their bulk counterparts. Therefore, dimensionality-controlled miniaturization of MOFs enables the customised use of nanoMOFs for specific applications where suitable size and shape are key prerequisites. In this feature article we survey the burgeoning field of nanoscale MOF synthesis, ranging from classical protocols such as microemulsion synthesis all the way to microfluidic-based techniques and template-directed epitaxial growth schemes. Along these lines, we will fathom the feasibility of rationally designing specific MOF nanomorphologies—zero-, one- and two-dimensional nanostructures—and we will explore more complex “second-generation” nanostructures typically evolving from a high level of interfacial control. As a recurring theme, we will review recent advances made toward the understanding of nucleation and growth processes at the nanoscale, as such insights are expected to further push the borders of nanoMOF science

Myelin insulation as a risk factor for axonal degeneration in autoimmune demyelinating disease

Axonal degeneration determines the clinical outcome of multiple sclerosis and is thought to result from exposure of denuded axons to immune-mediated damage. Therefore, myelin is widely considered to be a protective structure for axons in multiple sclerosis. Myelinated axons also depend on oligodendrocytes, which provide metabolic and structural support to the axonal compartment. Given that axonal pathology in multiple sclerosis is already visible at early disease stages, before overt demyelination, we reasoned that autoimmune inflammation may disrupt oligodendroglial support mechanisms and hence primarily affect axons insulated by myelin. Here, we studied axonal pathology as a function of myelination in human multiple sclerosis and mouse models of autoimmune encephalomyelitis with genetically altered myelination. We demonstrate that myelin ensheathment itself becomes detrimental for axonal survival and increases the risk of axons degenerating in an autoimmune environment. This challenges the view of myelin as a solely protective structure and suggests that axonal dependence on oligodendroglial support can become fatal when myelin is under inflammatory attack

Surfactant-directed syntheses of mesostructured zinc imidazolates: formation mechanism and structural insights

Supramolecular templating techniques have been widely used to direct the formation of porous materials with the goal of introducing permanent mesoporosity. While surfactant-directed self-assembly has been exploited for inorganic materials such as titania, silica, organosilica, and zeolites, it has rarely been applied to metal-organic frameworks (MOFs) and coordination polymers. Here we introduce a new family of gemini surfactant-directed zinc imidazolates, referred to as mesostructured imidazolate frameworks (MIFs), and present a detailed study on the influence of different gemini-type surfactants on the formation mechanism and structures of the resulting zinc imidazolates. The proposed formation mechanism for MIF-type materials involves co-assembly and crystallization processes that yield lamellar mesostructured imidazolate frameworks. Understanding and controlling such processes also has implications for the syntheses of microporous zinc imidazolate framework (ZIF) materials, whose formation can be suppressed in surfactant-rich solutions, whereas formation of MIF materials is favored in the presence of surfactants and triggered by the addition of halogenides. Solid-state 2D 13C1H HETCOR NMR measurements on prototypic CTAB-directed MIF-1 establish that the head group moieties of the surfactant molecules interact strongly with the zinc-imidazolate-bromide sheets. Additionally, the NMR analyses suggest that MIF-1 has a significant fraction of surfactant molecules that are interdigitated between the zinc-imidazolate-bromide sheets with an antiparallel stacking arrangement, consistent with the high thermal and chemical stability of the MIF hybrid materials