Chemistry of SURMOFs: layer-selective installation of functional groups and post-synthetic covalent modification probed by fluorescence microscopy.

Layer-selective installation of functional groups at SURMOFs (surface-attached metal-organic framework multilayers) is reported. Multilayers of [Cu(ndc)(dabco)(0.5)] grown in [001] orientation on pyridine-terminated organic self-assembled monolayers on Au substrates were functionalized with amino groups by step-by-step liquid-phase epitaxy. The method allows the growth of samples exhibiting one monolayer of functional groups at the external thin-film surface. In situ quartz crystal microbalance monitoring confirmed the presence of amino groups by turning the multilayer film from a non-reactive to a reactive material for covalent binding of fluoresceinisothiocyanate, and fluorescence microscopy displays the expected luminous property.

Liquid-phase epitaxy of multicomponent layer-based porous coordination polymer thin films of [M(L)(P)0.5] type: importance of deposition sequence on the oriented growth.

The progressive liquid-phase layer-by-layer (LbL) growth of anisotropic multicomponent layer-based porous coordination polymers (PCPs) of the general formula [M(L)(P)(0.5)] (M: Cu(2+), Zn(2+); L: dicarboxylate linker; P: dinitrogen pillar ligand) was investigated by using either pyridyl- or carboxyl-terminated self-assembled monolayers (SAMs) on gold substrates as templates. It was found that the deposition of smooth, highly crystalline, and oriented multilayer films of these PCPs depends on the conditions at the early growth cycles. In the case of a two-step process with an equimolar mixture of L and P, growth along the [001] direction is strongly preferred. However, employing a three-step scheme with full separation of all components allows deposition along the [100] direction on carboxyl-terminated SAMs. Interestingly, the growth of additional layers on top of previously grown oriented seeding layers proved to be insensitive to the particular growth scheme and full retention of the initial orientation, either along the [001] or [100] direction, was observed. This homo- and heteroepitaxial LbL growth allows full control over the orientation and the layer sequence, including introduction of functionalized linkers and pillars.

Surface chemistry of metal-organic frameworks at the liquid-solid interface.

Metal-organic frameworks (MOFs) are a fascinating class of novel inorganic-organic hybrid materials. They are essentially based on classic coordination chemistry and hold much promise for unique applications ranging from gas storage and separation to chemical sensing, catalysis, and drug release. The evolution of the full innovative potential of MOFs, in particular for nanotechnology and device integration, however requires a fundamental understanding of the formation process of MOFs. Also necessary is the ability to control the growth of thin MOF films and the positioning of size- and shape-selected crystals as well as MOF heterostructures on a given surface in a well-defined and oriented fashion. MOFs are solid-state materials typically formed by solvothermal reactions and their crystallization from the liquid phase involves the surface chemistry of their building blocks. This Review brings together various key aspects of the surface chemistry of MOFs.

Controlling interpenetration in metal-organic frameworks by liquid-phase epitaxy.

Metal-organic frameworks (MOFs) are highly porous materials generally consisting of two building elements: inorganic coupling units and organic linkers. These frameworks offer an enormous porosity, which can be used to store large amounts of gases and, as demonstrated in more recent applications, makes these compounds suitable for drug release. The huge sizes of the pores inside MOFs, however, also give rise to a fundamental complication, namely the formation of sublattices occupying the same space. This interpenetration greatly reduces the pore size and thus the available space within the MOF structure. We demonstrate here that the formation of the second, interpenetrated framework can be suppressed by using liquid-phase epitaxy on an organic template. This success demonstrates the potential of the step-by-step method to synthesize new classes of MOFs not accessible by conventional solvothermal methods.

Nanocrystals of [Cu3(btc)2] (HKUST-1): a combined time-resolved light scattering and scanning electron microscopy study.

The formation of [Cu(3)(btc)(2)] (HKUST-1; btc = 1,3,5-benzenetricarboxylate) nanocrystals from a super-saturated mother solution at room temperature was monitored by time-resolved light scattering (TLS); the system is characterized by a rapid growth up to a size limit of 200 nm within a few minutes, and the size and shape of the crystallites were also determined by scanning electron microscopy (SEM).

Growth mechanism of metal-organic frameworks: insights into the nucleation by employing a step-by-step route.

One step at a time: The in situ monitoring of the step-by-step formation of metal-organic frameworks (MOFs) by using surface plasmon resonance (SPR), allows the nucleation process and the formation of the secondary building units to be investigated. Growth rates on functionalized organic surfaces with different crystallographic orientations can also be studied.

Surface structure of metal-organic framework grown on self-assembled monolayers revealed by high-resolution atomic force microscopy.

The surface structure of an individual metal-organic framework (MOF) microcrystal grown on a functionalized surface has been successfully investigated for the first time in air and vacuum using high-resolution atomic force microscopy. Moreover, this detailed surface analysis has been utilized to optimize the MOF formation procedure to obtain a defect-free surface structure. Comparison of obtained data with recent microscopic studies performed on the same MOF crystal but grown by a conventional procedure clearly shows a much higher quality of crystals produced by surface oriented growth. Importantly, this method of preparing crystals suitable for microscopic analysis is also much faster (3 days compared to 2 years) and, in contrast to the conventional method, produces material suitable for in situ study. These results thus demonstrate for the first time the possibility of nanoscale investigation/modification of MOF surface structure.

Human guanylate-binding protein 1 as a model system investigated by several surface techniques.

In medical technologies concerning the surface immobilization of proteins in a defined orientation, maintaining their activity is a critical aspect. Therefore, in this study, the authors have investigated the activity of an elongated protein attached to a self-assembled monolayer supported streptavidin layer for different relative orientations of the protein with regard to the surface. Several mutants of this protein, human guanylate-binding protein 1 (hGBP1) showing GTPase catalytic activity, have been furnished with either one or two biotin anchors. Various independent methods that are based on different biophysical properties such as surface plasmon resonance, atomic force microscopy, and quartz crystal microbalance have been used to determine the orientation of the hGBP1 variants after anchoring them via a streptavidin-linker to a biotinylated surface. The activity of guanosine-triphosphate hydrolysis of hGBP1 monomers bound on the surface is found to depend on their orientation relative to the substrate, relating to their ability to form dimers with other neighboring anchored mutants; the maximum activity is lower than that observed in solutions, as might be expected from diffusion limitations at the solid/liquid interface on the one hand and prevention from homodimer formation due to immobilization on the other hand.

Thin films of metal-organic frameworks.

The fabrication of thin film coatings of metal-organic frameworks (MOFs) on various substrates is discussed in this critical review. Interestingly, the relatively few studies on MOF films that have appeared in the literature are limited to the following cases: [Zn4O(bdc)3] (MOF-5; bdc=1,4-benzenedicarboxylate), [Cu3(btc)2] (HKUST-1; btc=1,3,5-benzenetricarboxylate), [Zn2(bdc)2(dabco)] (dabco=1,4-diazabicyclo[2.2.2]octane), [Mn(HCOO)], [Cu2(pzdc)2(pyz)] (CPL-1; pzdc=pyrazine-2,3-dicarboxylate, pyz=pyrazine), [Fe(OH)(bdc)] (MIL-53(Fe)) and [Fe3O(bdc)3(Ac)] (MIL-88B; Ac=CH3COO-). Various substrates and support materials have been used, including silica, porous alumina, graphite and organic surfaces, i.e. self-assembled monolayers (SAMs) on gold, as well as silica surfaces. Most of the MOF films were grown by immersion of the selected substrates into specifically pre-treated solvothermal mother liquors of the particular MOF material. This results in more or less densely packed films of intergrown primary crystallites of sizes ranging up to several microm, leading to corresponding film thicknesses. Alternatively, almost atomically flat and very homogenous films, with thicknesses of up to ca. 100 nm, were grown in a novel stepwise layer-by-layer method. The individual growth steps are separated by removing unreacted components via rinsing the substrate with the solvent. The layer-by-layer method offers the possibility to study the kinetics of film formation in more detail using surface plasmon resonance. In some cases, particularly on SAM-modified substrates, a highly oriented growth was observed, and in the case of the MIL-53/MIL-88B system, a phase selective deposition of MIL-88B, rather than MIL-53(Fe), was reported. The growth of MOF thin films is important for smart membranes, catalytic coatings, chemical sensors and related nanodevices (63 references).