Functionalization of monolithic MOF thin films with hydrocarbon chains to achieve superhydrophobic surfaces with tunable water adhesion strength.

While the accessible pores render an enormous variety of functionalities to the bulk of metal-organic frameworks (MOFs), the outer surfaces exposed by these crystalline materials also offer unique characteristics not available when using conventional substrates. By grafting hydrocarbon chains to well-defined MOF thin films (SURMOFs) prepared using layer-by-layer methods, we were able to fabricate superhydrophobic substrates with static water contact angles over 160°. A detailed theoretical modelling of the hydrocarbon chains grafted on the outer SURMOF surface with well-defined spacing between anchoring points reveals that the grafted hydrocarbon chains behave similarly to polymer brushes during wetting, where conformational entropy is traded with mixing entropy.

Regulated Charge Transfer in Donor-Acceptor Metal-Organic Frameworks for Highly-Sensitive Photodetectors.

In photo-induced charge separation, organic thin films with donor and acceptor chromophores are vital for uses such as artificial photosynthesis and photodetection. The main challenges include optimizing charge separation efficiency and identifying the ideal acceptor/donor ratio. Achieving this is difficult due to the variability in molecular configurations within these typically amorphous organic aggregates.

Modulating the photolysis of aryl azides in a supramolecular host to develop photoactivatable fluorophores.

Photolysis of aryl azides is a convenient method to approach more functionalized systems in chemical biology. Here, we present a set of photoactivatable aryl azides that undergo controlled reaction pathways within the cucurbit[7]uril (CB7) cavity upon photolysis. The fluorescence turn-on process is utilized for bioimaging.

A simple method to modulate the selectivity of aryl azide photolysis using cucurbit[8]uril.

Photolysis of aryl azides typically involves multiple reaction pathways. This study designed and synthesized an aryl azide rotamer with two conformations. In aqueous media, its photolysis yields two main products.

The role of TiO and gCN bimetallic catalysts in boosting antibiotic resistance gene removal through photocatalyst assisted peroxone process.

Antibiotics are extensively used in human medicine, aquaculture, and animal husbandry, leading to the release of antimicrobial resistance into the environment. This contributes to the rapid spread of antibiotic-resistant genes (ARGs), posing a significant threat to human health and aquatic ecosystems. Conventional wastewater treatment methods often fail to eliminate ARGs, prompting the adoption of advanced oxidation processes (AOPs) to address this growing risk.

Integrating Biocatalysts into Metal-Organic Frameworks: Disentangling the Roles of Affinity, Molecular Weight, and Size.

The integration of biocatalysts within metal-organic frameworks (MOFs) is attracting growing interest due to its potential to both enhance biocatalyst stability and sustain biocatalyst activity in organic solvents. However, the factors that facilitate the post-synthetic infiltration of such large molecules into MOF pores remain unclear. This systematic study enabled the identification of the influence of biocatalyst molecular size, molecular weight and affinity on the uptake by an archetypal MOF, NU-1000.

Enhancing structural control in covalent organic frameworks through steric interaction-driven linker design.

Covalent Organic Frameworks (COFs) exhibiting kagome () structures are promising crystalline porous materials with two distinct pores. However, there are no reliable synthetic methods to exclusively target the over the polymorphic square-lattice () structure. To address this, we introduce a linker design strategy featuring bulky functional groups, which through steric interactions can hinder the net formation, thereby leading to a structure.

Inverse Vulcanization of Activated Norbornenyl Esters-A Versatile Platform for Functional Sulfur Polymers.

Elemental sulfur has shown to be a promising alternative feedstock for development of novel polymeric materials with high sulfur content. However, the utilization of inverse vulcanized polymers is restricted by the limitation of functional comonomers suitable for an inverse vulcanization. Control over properties and structure of inverse vulcanized polymers still poses a challenge to current research due to the dynamic nature of sulfur-sulfur bonds and high temperature of inverse vulcanization reactions.

Highly Active Oxidation Catalysts through Confining Pd Clusters on CeO Nano-Islands.

CeO-supported noble metal clusters are attractive catalytic materials for several applications. However, their atomic dispersion under oxidizing reaction conditions often leads to catalyst deactivation. In this study, the noble metal cluster formation threshold is rationally adjusted by using a mixed CeO-AlO support.

Structure and Chemical Reactivity of Y-Stabilized ZrO Surfaces: Importance for the Water-Gas Shift Reaction.

The surface structure and chemical properties of Y-stabilized zirconia (YSZ) have been subjects of intense debate over the past three decades. However, a thorough understanding of chemical processes occurring at YSZ powders faces significant challenges due to the absence of reliable reference data acquired for well-controlled model systems. Here, we present results from polarization-resolved infrared reflection absorption spectroscopy (IRRAS) obtained for differently oriented, Y-doped ZrO single-crystal surfaces after exposure to CO and DO.

Study of rutile TiO(110) single crystal by transient absorption spectroscopy in the presence of Cecations in aqueous environment. Implication on water splitting.

Cecations are commonly used as electron acceptors during the water oxidation to Oreaction over Ir- and Ru-based catalysts. They can also be reduced to Cecations by excited electrons from the conduction band of an oxide semiconductor with a suitable energy level. In this work, we have studied their interaction with a rutile TiO(110) single crystal upon band gap excitation by femtosecond transient absorption spectroscopy (TAS) in solution in the 350-900 nm range and up to 3.

A Versatile Microfluidic Platform for Extravasation Studies Based on DNA Origami-Cell Interactions.

The adhesion of circulating tumor cells (CTCs) to the endothelial lumen and their extravasation to surrounding tissues are crucial in the seeding of metastases and remain the most complex events of the metastatic cascade to study. Integrins expressed on CTCs are major regulators of the extravasation process. This knowledge is primarily derived from animal models and biomimetic systems based on artificial endothelial layers, but these methods have ethical or technical limitations.

Classification and Identification of Perfume Scents by an Enantioselective Colorimetric Sensor Array of Chiral Metal-Organic-Framework-Based Fabry-Pérot Films.

Many odors, like perfumes, are complex mixtures of chiral and achiral molecules where the cost-efficient (enantio-)selective sensing represents a major technical challenge. Here, we present a colorimetric sensor array of surface-mounted metal-organic-framework (SURMOF) films in Fabry-Pérot (FP) cavities. The optical properties of the FP-SURMOF films with different chiral and achiral structures are affected by the (enantio-)selective adsorption of the analytes in the SURMOF pores, resulting in different responses to the analyte molecules.

One-step sputtering of MoSSe metastable phase as thin film and predicted thermodynamic stability by computational methods.

We present the fabrication of a MoSSe thin film from a co-sputtering process using MoS and MoSe commercial targets with 99.9% purity. The sputtering of the MoS and MoSe was carried out using a straight and low-cost magnetron radio frequency sputtering recipe to achieve a MoSSe phase with x = 1 and sharp interface formation as confirmed by Raman spectroscopy, time-of-flight secondary ion mass spectroscopy, and cross-sectional scanning electron microscopy.

Ultrastrong Electron-Phonon Coupling in Uranium-Organic Frameworks Leading to Inverse Luminescence Temperature Dependence.

Electron-phonon interactions, crucial in condensed matter, are rarely seen in Metal-Organic Frameworks (MOFs). Detecting these interactions typically involves analyzing luminescence in lanthanide- or actinide-based compounds. Prior studies on Ln- and Ac-based MOFs at high temperatures revealed additional peaks, but these were too faint for thorough analysis.

Photoswitchable Radical State in Nanoporous Metal-Organic Framework Films with Embedded Hexaarylbiimidazole.

Photoresponsive materials enable dynamic remote control of their fundamental properties. The incorporation of photochromic molecules in nanoporous metal-organic frameworks (MOFs) provides a unique opportunity to tailor the material properties, including the interaction between the MOF host and guest molecules in the pores. Here, a MOF film of type HKUST-1 with embedded hexaarylbiimidazole (HABI), undergoing reversible light-induced reactions between the stable dimer state and the metastable radical state, is presented.

On-off conduction photoswitching in modelled spiropyran-based metal-organic frameworks.

Materials with photoswitchable electronic properties and conductance values that can be reversibly changed over many orders of magnitude are highly desirable. Metal-organic framework (MOF) films functionalized with photoresponsive spiropyran molecules demonstrated the general possibility to switch the conduction by light with potentially large on-off-ratios. However, the fabrication of MOF materials in a trial-and-error approach is cumbersome and would benefit significantly from in silico molecular design.

Modulating Aryl Azide Photolysis: Synthesis of a Room-Temperature Phosphorescent Carboline in Cucurbit[7]uril Host.

Cucurbit[7]uril (CB7), a supramolecular host, is employed to control the pathway of photolysis of an aryl azide in an aqueous medium. Normally, photolysis of aryl azides in bulk water culminates predominantly in the formation of azepine derivatives via intramolecular rearrangement. Remarkably, however, when this process unfolds within the protective confinement of the CB7 cavity, it results in a carboline derivative, as a consequence of a C─H amination reaction.

Antibiotic resistances from slaughterhouse effluents and enhanced antimicrobial blue light technology for wastewater decontamionation.

The frequencies of 6 different facultative pathogenic bacteria of the ESKAPE group (priority list WHO) and a total of 14 antibiotic resistance genes (ARGs) with different priorities for human medicine were quantified in wastewaters of poultry and pig slaughterhouses using molecular biological approaches. Raw sewage from poultry and pig slaughterhouses was found to be contaminated not only with facultative pathogenic bacteria but also with various categories of clinically relevant ARGs, including ARGs against the reserve antibiotics group. The concentration of the different gene targets decreased after on-site conventional biological or advanced oxidative wastewater treatments, but was not eliminated.

MOFGalaxyNet: a social network analysis for predicting guest accessibility in metal-organic frameworks utilizing graph convolutional networks.

Metal-organic frameworks (MOFs), are porous crystalline structures comprising of metal ions or clusters intricately linked with organic entities, displaying topological diversity and effortless chemical flexibility. These characteristics render them apt for multifarious applications such as adsorption, separation, sensing, and catalysis. Predominantly, the distinctive properties and prospective utility of MOFs are discerned post-manufacture or extrapolation from theoretically conceived models.

Nano- and Microscale Confinements in DNA-Scaffolded Enzyme Cascade Reactions.

Artificial reconstruction of naturally evolved principles, such as compartmentalization and cascading of multienzyme complexes, offers enormous potential for the development of biocatalytic materials and processes. Due to their unique addressability at the nanoscale, DNA origami nanostructures (DON) have proven to be an exceptionally powerful tool for studying the fundamental processes in biocatalytic cascades. To systematically investigate the diffusion-reaction network of (co)substrate transfer in enzyme cascades, a model system of stereoselective ketoreductase (KRED) with cofactor regenerating enzyme is assembled in different spatial arrangements on DNA nanostructures and is located in the sphere of microbeads (MB) as a spatially confining nano- and microenvironment, respectively.

Free-floating extracellular DNA (exDNA) in different wastewaters: Status quo on exDNA-associated antimicrobial resistance genes.

Wastewater treatment plants (WWTPs) have been reported as major anthropogenic reservoirs for the spread of antibiotic-resistant bacteria (ARB) and antibiotic resistance genes (ARGs) into the environment, worldwide. While most studies mainly focus on the intracellular DNA (iDNA), extracellular DNA (exDNA) accounting for a significant proportion of the total DNA in wastewater, was usually neglected. Following the One Health approach, this study focuses on wastewaters of municipal, clinical, and livestock origins (n = 45) that undergo different treatment processes (i.

Enhancing Sustainable Production of Fatty Acid Methyl Ester from Palm Oil Using Bio-Based Heterogeneous Catalyst: Process Simulation and Techno-Economic Analysis.

A new sustainable solid carbon catalyst has been developed for biodiesel synthesis using pyrolytic coconut shell ash (CSA). The CSA support was loaded with various amounts of potassium carbonate (KCO), and response surface methodology with a central composite design was used to optimize the transesterification process. The best-performing catalyst was the 30 wt % KCO/CSA catalyst.

Tunable J-type aggregation of silicon phthalocyanines in a surface-anchored metal-organic framework thin film.

Organic chromophores and semiconductors, like anthracene, pentacene, perylene, and porphyrin, are prone to aggregation, and their packing in the solid state is often hard to predict and difficult to control. As the condensed phase structures of these chromophores and semiconductors are of crucial importance for their optoelectronic functionality, strategies to control their assembly and provide new structural motifs are important. One such approach uses metal-organic frameworks (MOFs); the organic chromophore is converted into a linker and connected by metal ions or nodes.