Dynamic Surface Modification of Metal-Organic Framework Nanoparticles via Alkoxyamine Functional Groups.

External surface engineering of metal-organic framework nanoparticles (MOF NPs) is emerging as an important design strategy, leading to optimized chemical and colloidal stability. To date, most of the MOF surface modifications have been performed either by physical adsorption or chemical association of small molecules or (preformed) polymers. However, most of the currently employed approaches cannot precisely control the polymer density, and dynamic modifications at the surfaces on demand have been a challenging task. Here, we introduce a general approach based on covalent modification employing alkoxyamines as a versatile tool to modify the outer surface of MOF nanoparticles (NPs). The alkoxyamines serve as initiators to grow polymers from the MOF surface via nitroxide-mediated polymerization (NMP) and allow dynamic attachment of small molecules via a nitroxide exchange reaction (NER). The successful surface modification and successive surface polymerization are confirmed via time-of-flight secondary ion mass spectrometry (ToF-SIMS), size exclusion chromatography (SEC), and nuclear magnetic resonance (NMR) spectroscopy. The functionalized MOF NPs exhibit high suspension stability and good dispersibility while retaining their chemical integrity and crystalline structure. In addition, electron paramagnetic resonance spectroscopy (EPR) studies prove the dynamic exchange of two different nitroxide species via NER and further allow us to quantify the surface modification with high sensitivity. Our results demonstrate that alkoxyamines serve as a versatile tool to dynamically modify the surface of MOF NPs with high precision, allowing us to tailor their properties for a wide range of potential applications, such as drug delivery or mixed matrix membranes.

MOFSocialNet: Exploiting Metal-Organic Framework Relationships via Social Network Analysis.

The number of metal-organic frameworks (MOF) as well as the number of applications of this material are growing rapidly. With the number of characterized compounds exceeding 100,000, manual sorting becomes impossible. At the same time, the increasing computer power and established use of automated machine learning approaches makes data science tools available, that provide an overview of the MOF chemical space and support the selection of suitable MOFs for a desired application. Among the different data science tools, graph theory approaches, where data generated from numerous real-world applications is represented as a graph (network) of interconnected objects, has been widely used in a variety of scientific fields such as social sciences, health informatics, biological sciences, agricultural sciences and economics. We describe the application of a particular graph theory approach known as social network analysis to MOF materials and highlight the importance of community (group) detection and graph node centrality. In this first application of the social network analysis approach to MOF chemical space, we created MOFSocialNet. This social network is based on the geometrical descriptors of MOFs available in the CoRE-MOFs database. MOFSocialNet can discover communities with similar MOFs structures and identify the most representative MOFs within a given community. In addition, analysis of MOFSocialNet using social network analysis methods can predict MOF properties more accurately than conventional ML tools. The latter advantage is demonstrated for the prediction of gas storage properties, the most important property of these porous reticular networks.

MOF Synthesis Prediction Enabled by Automatic Data Mining and Machine Learning.

Despite rapid progress in the field of metal-organic frameworks (MOFs), the potential of using machine learning (ML) methods to predict MOF synthesis parameters is still untapped. Here, we show how ML can be used for rationalization and acceleration of the MOF discovery process by directly predicting the synthesis conditions of a MOF based on its crystal structure. Our approach is based on: i) establishing the first MOF synthesis database via automatic extraction of synthesis parameters from the literature, ii) training and optimizing ML models by employing the MOF database, and iii) predicting the synthesis conditions for new MOF structures. The ML models, even at an initial stage, exhibit a good prediction performance, outperforming human expert predictions, obtained through a synthesis survey. The automated synthesis prediction is available via a web-tool on https://mof-synthesis.aimat.science.

Performance Fabrics Obtained by In Situ Growth of Metal-Organic Frameworks in Electrospun Fibers.

Metal-organic frameworks (MOFs) exhibit an exceptional surface area-to-volume ratio, variable pore sizes, and selective binding, and hence, there is an ongoing effort to advance their processability for broadening their utilization in different applications. In this work, we demonstrate a general scheme for fabricating freestanding MOF-embedded polymeric fibers, in which the fibers themselves act as microreactors for the in situ growth of the MOF crystals. The MOF-embedded fibers are obtained via a two-step process, in which, initially, polymer solutions containing the MOF precursors are electrospun to obtain microfibers, and then, the growth of MOF crystals is initiated and performed via antisolvent-induced crystallization. Using this approach, we demonstrate the fabrication of composite microfibers containing two types of MOFs: copper (II) benzene-1,3,5-tricarboxylic acid (HKUST-1) and zinc (II) 2-methylimidazole (ZIF-8). The MOF crystals grow from the fiber's core toward its outer rims, leading to exposed MOF crystals that are well rooted within the polymer matrix. The MOF fibers obtained using this method can reach lengths of hundreds of meters and exhibit mechanical strength that allows arranging them into dense, flexible, and highly durable nonwoven meshes. We also examined the use of the MOF fiber meshes for the immobilization of the enzymes catalase and horse radish peroxidase (HRP), and the enzyme-MOF fabrics exhibit improved performance. The MOF-embedded fibers, demonstrated in this work, hold promise for different applications including separation of specific chemical species, selective catalysis, and sensing and pave the way to new MOF-containing performance fabrics and active membranes.

Current Trends in Metal-Organic and Covalent Organic Framework Membrane Materials.

Metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) have been thoroughly investigated with regards to applications in gas separation membranes in the past years. More recently, new preparation methods for MOFs and COFs as particles and thin-film membranes, as well as for mixed-matrix membranes (MMMs) have been developed. We will highlight novel processes and highly functional materials: Zeolitic imidazolate frameworks (ZIFs) can be transformed into glasses and we will give an insight into their use for membranes. In addition, liquids with permanent porosity offer solution processability for the manufacture of extremely potent MMMs. Also, MOF materials influenced by external stimuli give new directions for the enhancement of performance by in situ techniques. Presently, COFs with their large pores are useful in quantum sieving applications, and by exploiting the stacking behavior also molecular sieving COF membranes are possible. Similarly, porous polymers can be constructed using MOF templates, which then find use in gas separation membranes.

Dynamic porous organic polymers with tuneable crosslinking degree and porosity.

Porous organic polymers (POPs) show enormous potential for applications in separation, organic electronics, and biomedicine due to the combination of high porosity, high stability, and ease of functionalisation. However, POPs are usually insoluble and amorphous materials making it very challenging to obtain structural information. Additionally, important parameters such as the exact molecular structure or the crosslinking degree are largely unknown, despite their importance for the final properties of the system. In this work, we introduced the reversible multi-fold nitroxide exchange reaction to the synthesis of POPs to tune and at the same time follow the crosslinking degree in porous polymer materials. We synthesised three different POPs based on the combination of linear, trigonal, and tetrahedral alkoxyamines with a tetrahedral nitroxide. We could show that modulating the equilibrium in the nitroxide exchange reaction, by adding or removing one nitroxide species, leads to changes in the crosslinking degree. Being able to modulate the crosslinking degree in POPs allowed us to investigate both the influence of the crosslinking degree and the structure of the molecular components on the porosity. The crosslinking degree of the frameworks was characterised using EPR spectroscopy and the porosity was determined using argon gas adsorption measurements. To guide the design of POPs for desired applications, our study reveals that multiple factors need to be considered such as the structure of the molecular building blocks, the synthetic conditions, and the crosslinking degree.

Design of Metal-Organic Framework Templated Materials Using High-Throughput Computational Screening.

The ability to crosslink Metal-Organic Frameworks (MOFs) has recently been discovered as a flexible approach towards synthesizing MOF-templated "ideal network polymers". Crosslinking MOFs with rigid cross-linkers would allow the synthesis of crystalline Covalent-Organic Frameworks (COFs) of so far unprecedented flexibility in network topologies, far exceeding the conventional direct COF synthesis approach. However, to date only flexible cross-linkers were used in the MOF crosslinking approach, since a rigid cross-linker would require an ideal fit between the MOF structure and the cross-linker, which is experimentally extremely challenging, making in silico design mandatory. Here, we present an effective geometric method to find an ideal MOF cross-linker pair by employing a high-throughput screening approach. The algorithm considers distances, angles, and arbitrary rotations to optimally match the cross-linker inside the MOF structures. In a second, independent step, using Molecular Dynamics (MD) simulations we quantitatively confirmed all matches provided by the screening. Our approach thus provides a robust and powerful method to identify ideal MOF/Cross-linker combinations, which helped to identify several MOF-to-COF candidate structures by starting from suitable libraries. The algorithms presented here can be extended to other advanced network structures, such as mechanically interlocked materials or molecular weaving and knots.

Polymerization in MOF-Confined Nanospaces: Tailored Architectures, Functions, and Applications.

This feature article describes recent trends and advances in structuring network polymers using a coordination-driven metal-organic framework (MOF)-based template approach to demonstrate the concept of crystal-controlled polymerization in confined nanospaces, forming tailored architectures ranging from simple linear one-dimensional macromolecules to tunable three-dimensional cross-linked network polymers and interwoven molecular architectures. MOF-templated network polymers combine the characteristics and advantages of crystalline MOFs (high porosity, structural regularity, and designability) with the intrinsic behaviors of soft polymers (flexibility, processability, stability, or biocompatibility) with widespread application possibilities and tunable properties. The article ends with a summary of the remaining challenges to be addressed, and future research opportunities in this field are discussed.

Synthesis, Transfer, and Gas Separation Characteristics of MOF-Templated Polymer Membranes.

This paper discusses the potential of polymer networks, templated by crystalline metal-organic framework (MOF), as novel selective layer material in thin film composite membranes. The ability to create mechanically stable membranes with an ultra-thin selective layer of advanced polymer materials is highly desirable in membrane technology. Here, we describe a novel polymeric membrane, which is synthesized via the conversion of a surface anchored metal-organic framework (SURMOF) into a surface anchored gel (SURGEL). The SURGEL membranes combine the high variability in the building blocks and the possibility to control the network topology and membrane thickness of the SURMOF synthesis with high mechanical and chemical stability of polymers. Next to the material design, the transfer of membranes to suitable supports is also usually a challenging task, due to the fragile nature of the ultra-thin films. To overcome this issue, we utilized a porous support on top of the membrane, which is mechanically stable enough to allow for the easy membrane transfer from the synthesis substrate to the final membrane support. To demonstrate the potential for gas separation of the synthesized SURGEL membranes, as well as the suitability of the transfer method, we determined the permeance for eight gases with different kinetic diameters.

Rising Up: Hierarchical Metal-Organic Frameworks in Experiments and Simulations.

Controlled synthesis across several length scales, ranging from discrete molecular building blocks to size- and morphology-controlled nanoparticles to 2D sheets and thin films and finally to 3D architectures, is an advanced and highly active research field within both the metal-organic framework (MOF) domain and the overall material science community. Along with synthetic progress, theoretical simulations of MOF structures and properties have shown tremendous progress in both accuracy and system size. Further advancements in the field of hierarchically structured MOF materials will allow the optimization of their performance; however, this optimization requires a deep understanding of the different synthesis and processing techniques and an enhanced implementation of material modeling. Such modeling approaches will allow us to select and synthesize the highest-performing structures in a targeted rational manner. Here, recent progress in the synthesis of hierarchically structured MOFs and multiscale modeling and associated simulation techniques is presented, along with a brief overview of the challenges and future perspectives associated with a simulation-based approach toward the development of advanced hierarchically structured MOF materials.

Metal-Organic Framework-Templated Biomaterials: Recent Progress in Synthesis, Functionalization, and Applications.

The integration of a porous crystalline framework with soft polymers to create novel biomaterials has tremendous potential yet remains very challenging to date. Metal-organic framework (MOF)-templated polymers (MTPs) have emerged as persistent modular materials that can be tailored for desired biofunctions. These represent a novel class of hierarchically structured assemblies that combine the advantages of MOFs (precisely controlled structure, enormous diversity in framework topology, and high porosity) with the intrinsic behaviors of polymers (soft texture, flexibility, biocompatibility, and improved stability under physiological conditions). Transformation of surface-anchored MOFs (SURMOFs) via orthogonal covalent cross-linking yields surface-anchored polymeric gels (SURGELs) that open up exciting new opportunities to create soft nanoporous materials. SURGELs overcome the main drawbacks of SURMOFs, such as their limited stability under physiological conditions and their potential to release toxic metal ions, a substantial problem for applications in life sciences. MOF (SURMOF)-templated polymerization processes control the synthesis on a molecular level. Additionally, the morphology of the original MOF crystal template is replicated in the final network polymers. The MOF-templated polymerization can be induced by light, a catalyst, or temperature using several types of reactions, including thiol-ene, metal-free alkyne-azide click reactions, and Glaser-Hay coupling. In the case of photoinduced reactions, the cross-linking process can be locally confined, allowing control of the macroscopic patterning of the resulting network polymer. The use of layer-by-layer (lbl) techniques in the SURMOF synthesis serves the purpose of precise, layer-selective incorporation of functionalities via the combination of the postsynthetic modification and heteroepitaxy strategies. Transforming the functionalized SURMOF into a SURGEL allows the fabrication of polymers with desired bioactive functions at the internal or external surfaces. This Account highlights our ongoing research and inspiring progress in transforming SURMOFs into persistent, modular nanoporous materials tailored with biofunctions. Using cell culture studies, we present various aspects of SURGEL materials, such as the ability to deliver bioactive molecules to adhering cells on SURGEL surfaces, applications to advanced drug delivery systems, the ability to tune cell adhesion via surface modification, and the development of porphyrin-based SURGEL thin films with antimicrobial properties. Then we critically examine the challenges and limitations of current systems and discuss future research directions and new approaches for advancing MOF-templated biocompatible materials, emphasizing the need to include responsive and adaptive functionalities into the system. We emphasize that the hierarchical structure, ranging from the molecular to the macroscopic scale, allows for optimization of the material properties across all length scales relevant for cell-material interactions.

Self-reporting and refoldable profluorescent single-chain nanoparticles.

We pioneer the formation of self-reporting and refoldable profluorescent single-chain nanoparticles (SCNPs) via the light-induced reaction (λmax = 320 nm) of nitroxide radicals with a photo-active crosslinker. Whereas the tethered nitroxide moiety in these polymers fully quenches the luminescence (i.e. fluorescence) of the aromatic backbone, nitroxide trapping of a transient C-radical leads to the corresponding closed shell alkoxyamine thereby restoring luminescence of the folded SCNP. Hence, the polymer in the folded state is capable of emitting light, while in the non-folded state the luminescence is silenced. Under oxidative conditions the initially folded SCNPs unfold, resulting in luminescence switch-off and the reestablishment of the initial precursor polymer. Critically, we show that the luminescence can be repeatedly silenced and reactivated. Importantly, the self-reporting character of the SCNPs was followed by size-exclusion chromatography (SEC), dynamic light scattering (DLS), fluorescence, electron paramagnetic resonance (EPR), nuclear magnetic resonance (NMR) and diffusion ordered NMR spectroscopy (DOSY).

High Antimicrobial Activity of Metal-Organic Framework-Templated Porphyrin Polymer Thin Films.

Development of surface coatings with high antimicrobial activity is urgently required to fight bacteria and other microorganisms on technical and hygiene relevant surfaces. Control over structure and topology of the surface coatings, combined with the ability to include functional molecules within the structure, is crucial for optimizing their performance. Herein, we describe a novel strategy to synthesize structurally well-defined porphyrin polymer thin films via a template approach. In this approach, bisazido-functionalized porphyrin molecules are preorganized within a metal-organic framework (MOF) structure. Afterward, porphyrin units within the MOF are covalently connected via a secondary linker. Removal of the metal ions of the MOF results in water-stable porphyrin polymer thin films that demonstrate high antibacterial activity against pathogens via visible-light-promoted generation of reactive oxygen species. In addition, this approach offers the inherent possibility to incorporate guest molecules within the structures, to functionalize the surface with biomolecules, and to create hierarchically structured materials.

Excitonically Coupled States in Crystalline Coordination Networks.

When chromophores are brought into close proximity, noncovalent interactions (π-π/CH-π) can lead to the formation of excitonically coupled states, which bestow new photophysical properties upon the aggregates. Because the properties of the new states not only depend on the strength of intermolecular interactions, but also on the relative orientation, supramolecular assemblies, where these parameters can be varied in a deliberate fashion, provide novel possibilities for the control of photophysical properties. This work reports that core-substituted naphthalene diimides (cNDIs) can be incorporated into surface-mounted metal- organic structures/frameworks (SURMOFs) to yield optical properties strikingly different from conventional aggregates of such molecules, for example, formed in solution or by crystallization. Organic linkers are used, based on cNDIs, well-known organic chromophores with numerous applications in different optoelectronic devices, to fabricate MOF thin films on transparent substrates. A thorough characterization of the properties of these highly ordered chromophoric assemblies reveals the presence of non-emissive excited states in the crystalline material. Structural modulations provide further insights into the nature of the coupling that gives rise to an excited-state energy level in the periodic structure.

Fast and efficient synthesis of microporous polymer nanomembranes via light-induced click reaction.

Conjugated microporous polymers (CMPs) are materials of low density and high intrinsic porosity. This is due to the use of rigid building blocks consisting only of lightweight elements. These materials are usually stable up to temperatures of 400 °C and are chemically inert, since the networks are highly crosslinked via strong covalent bonds, making them ideal candidates for demanding applications in hostile environments. However, the high stability and chemical inertness pose problems in the processing of the CMP materials and their integration in functional devices. Especially the application of these materials for membrane separation has been limited due to their insoluble nature when synthesized as bulk material. To make full use of the beneficial properties of CMPs for membrane applications, their synthesis and functionalization on surfaces become increasingly important. In this respect, we recently introduced the solid liquid interfacial layer-by-layer (LbL) synthesis of CMP-nanomembranes via Cu catalyzed azide-alkyne cycloaddition (CuAAC). However, this process featured very long reaction times and limited scalability. Herein we present the synthesis of surface grown CMP thin films and nanomembranes via light induced thiol-yne click reaction. Using this reaction, we could greatly enhance the CMP nanomembrane synthesis and further broaden the variability of the LbL approach.

Layer-by-layer Synthesis and Transfer of Freestanding Conjugated Microporous Polymer Nanomembranes.

CMP as large surface area materials have attracted growing interest recently, due to their high variability in the incorporation of functional groups in combination with their outstanding thermal and chemical stability, and low densities. However, their insoluble nature causes problems in their processing since usually applied techniques such as spin coating are not available. Especially for membrane applications, where the processing of CMP as thin films is desirable, the processing problems have hindered their commercial application. Here we describe the interfacial synthesis of CMP thin films on functionalized substrates via molecular layer-by-layer (l-b-l) synthesis. This process allows the preparation of films with desired thickness and composition and even desired composition gradients. The use of sacrificial supports allows the preparation of freestanding membranes by dissolution of the support after the synthesis. To handle such ultra-thin freestanding membranes the protection with sacrificial coatings showed great promise, to avoid rupture of the nanomembranes. To transfer the nanomembranes to the desired substrate, the coated membranes are upfloated at the air-liquid interface and then transferred via dip coating.

Hierarchically functionalized magnetic core/multishell particles and their postsynthetic conversion to polymer capsules.

The controlled synthesis of hierarchically functionalized core/multishell particles is highly desirable for applications in medicine, catalysis, and separation. Here, we describe the synthesis of hierarchically structured metal-organic framework multishells around magnetic core particles (magMOFs) via layer-by-layer (LbL) synthesis. The LbL deposition enables the design of multishell systems, where each MOF shell can be modified to install different functions. Here, we used this approach to create controlled release capsules, in which the inner shell serves as a reservoir and the outer shell serves as a membrane after postsynthetic conversion of the MOF structure to a polymer network. These capsules enable the controlled release of loaded dye molecules, depending on the surrounding media.

Fabrication of highly uniform gel coatings by the conversion of surface-anchored metal-organic frameworks.

We report the fabrication of 3D, highly porous, covalently bound polymer films of homogeneous thickness. These surface-bound gels combine the advantages of metal-organic framework (MOF) materials, namely, the enormous flexibility and the large size of the maximum pore structures and, in particular, the possibility to grow them epitaxially on modified substrates, with those of covalently connected gel materials, namely, the absence of metal ions in the deposited material, a robust framework consisting of covalent bonds, and, most importantly, pronounced stability under biological conditions. The conversion of a SURMOF (surface-mounted MOF) yields a surface-grafted gel. These SURGELs can be loaded with bioactive compounds and applied as bioactive coatings and provide a drug-release platform in in vitro cell culture studies.

Impact of molecular clustering inside nanopores on desorption processes.

Understanding the sorption kinetics of nanoporous systems is crucial for the development and design of novel porous materials for practical applications. Here, using a porous coordination polymer/quartz crystal microbalance (PCP/QCM) hybrid device, we investigate the desorption of various vapor molecules featuring different degrees of intermolecular (hydrogen bonding) or molecule-framework interactions. Our findings reveal that strong intermolecular interactions lead to the desorption process proceeding via an unprecedented metastable state, wherein the guest molecules are clustered within the pores, causing the desorption rate to be temporarily slowed. The results demonstrate the considerable impact of the chemical nature of an adsorbate on the kinetics of desorption, which is also expected to influence the efficiency of certain processes, such as desorption by gas purge.

Internalization pathways of anisotropic disc-shaped zeolite L nanocrystals with different surface properties in HeLa cancer cells.

Information about the mechanisms underlying the interactions of nanoparticles with living cells is crucial for their medical application and also provides indications of the putative toxicity of such materials. Here the uptake and intracellular delivery of disc-shaped zeolite L nanocrystals as porous aminosilicates with well-defined crystal structure, uncoated as well as with COOH-, NH2 -, polyethyleneglycol (PEG)- and polyallylamine hydrochloride (PAH) surface coatings are reported. HeLa cells are used as a model system to demonstrate the relation between these particles and cancer cells. Interactions are studied in terms of their fates under diverse in vitro cell culture conditions. Differently charged coatings demonstrated dissimilar behavior in terms of agglomeration in media, serum protein adsorption, nanoparticle cytotoxicity and cell internalization. It is also found that functionalized disc-shaped zeolite L particles enter the cancer cells via different, partly not yet characterized, pathways. These in vitro results provide additional insight about low-aspect ratio anisotropic nanoparticle interactions with cancer cells and demonstrate the possibility to manipulate the interactions of nanoparticles and cells by surface coating for the use of nanoparticles in medical applications.