Tuning UV Absorption in Imine-Linked Covalent Organic Frameworks via Methylation.

Covalent organic frameworks (COFs) are porous materials with high surface areas, making them interesting for a large variety of applications including energy storage, gas separation, photocatalysis, and chemical sensing. Structural variation plays an important role in tuning COF properties. Next to the type of the building block core, bonding directionality, and linking chemistry, substitution of building blocks provides another level of synthetic control. Thorough characterization and comparison of various substitution patterns is relevant for the molecular engineering of COFs via rational design. To this end, we have systematically synthesized and characterized multiple combinations of several methylated and non-methylated building blocks to obtain a series of imine-based COFs. This includes the experimental assignment of the COF structure by solid-state NMR. By comparing the properties of all COFs, the following trends were found: (1) upon methylation of the aldehyde nodes, COFs show increased Brunauer-Emmett-Teller surface areas, reduced pore collapse, blue-shifted absorbance spectra, and ∼0.2 eV increases in their optical band gaps. (2) COFs with dimethylated amine linkers show a lower porosity. (3) In tetramethylated amine linkers, the COF porosity even further decreases, the absorbance spectra are clearly red-shifted, and smaller optical band gaps are obtained. Our study shows that methyl substitution patterns on COF building blocks are a handle to control the UV absorbance of the resulting frameworks.

PUFA-Derived N-Acylethanolamide Probes Identify Peroxiredoxins and Small GTPases as Molecular Targets in LPS-Stimulated RAW264.7 Macrophages.

We studied the mechanistic and biological origins of anti-inflammatory poly-unsaturated fatty acid-derived N-acylethanolamines using synthetic bifunctional chemical probes of docosahexaenoyl ethanolamide (DHEA) and arachidonoyl ethanolamide (AEA) in RAW264.7 macrophages stimulated with 1.0 µg mL-1 lipopolysaccharide. Using a photoreactive diazirine, probes were covalently attached to their target proteins, which were further studied by introducing a fluorescent probe or biotin-based affinity purification. Fluorescence confocal microscopy showed DHEA and AEA probes localized in cytosol, specifically in structures that point toward the endoplasmic reticulum and in membrane vesicles. Affinity purification followed by proteomic analysis revealed peroxiredoxin-1 (Prdx1) as the most significant binding interactor of both DHEA and AEA probes. In addition, Prdx4, endosomal related proteins, small GTPase signaling proteins, and prostaglandin synthase 2 (Ptgs2, also known as cyclooxygenase 2 or COX-2) were identified. Lastly, confocal fluorescence microscopy revealed the colocalization of Ptgs2 and Rac1 with DHEA and AEA probes. These data identified new molecular targets suggesting that DHEA and AEA may be involved in reactive oxidation species regulation, cell migration, cytoskeletal remodeling, and endosomal trafficking and support endocytosis as an uptake mechanism.

Enhanced surface area and reduced pore collapse of methylated, imine-linked covalent organic frameworks.

Covalent Organic Frameworks (COFs) are thermally and chemically stable, nanoporous materials with high surface areas, making them interesting for a large variety of applications including energy storage, gas separation, catalysis and chemical sensing. However, pore blocking and pore collapse may limit their performance. Reducing the capillary forces by using solvents with low surface tension, like supercritical CO2, for activation, and the introduction of bulky isopropyl/methoxy groups were found to reduce pore collapse. Herein, we present an easy-to-use alternative that involves the combination of a new, methylated building block (2,4,6-trimethylbenzene-1,3,5-tricarbaldehyde, Me3TFB) with vacuum drying. Condensation of Me3TFB with 1,4-phenylenediamine (PA) or benzidine (BD) resulted in imine-linked 2D COFs (Me3TFB-PA and Me3TFB-BD) with higher degrees of crystallinity and higher BET surface areas compared to their non-methylated counterparts (TFB-PA and TFB-BD). This was rationalized by density functional theory computations. Additionally, the methylated COFs are less prone to pore collapse when subjected to vacuum drying and their BET surface area was found to remain stable for at least four weeks. Within the context of their applicability as sensors, we also studied the influence of hydrochloric acid vapour on the optical and structural properties of all COFs. Upon acid exposure their colour and absorbance spectra changed, making them indeed suitable for acid detection. Infrared spectroscopy revealed that the colour change is likely attributed to the cleavage of imine bonds, which are only partially restored after ammonia exposure. While this limits their application as reusable sensors, our work presents a facile method to increase the robustness of commonly known COFs.