Switching from Molecules to Functional Materials: Breakthroughs in Photochromism With MOFs.

Photochromic materials with properties that can be dynamically tailored as a function of external stimuli are a rapidly expanding field driven by applications in areas ranging from molecular computing, nanotechnology, or photopharmacology to programable heterogeneous catalysis. Challenges arise, however, when translating the rapid, solution-like response of stimuli-responsive moieties to solid-state materials due to the intermolecular interactions imposed through close molecular packing in bulk solids. As a result, the integration of photochromic compounds into synthetically programable porous matrices, such as metal-organic frameworks (MOFs), has come to the forefront as an emerging strategy for photochromic material development.

Antiviral effects of umbelliferone against viral hemorrhagic septicemia virus in olive flounder (Paralichthys olivaceus).

Viral hemorrhagic septicemia virus (VHSV) poses a significant threat to global aquaculture, prompting ongoing efforts to identify potential drug candidates for disease prevention. Coumarin derivatives have recently emerged as a promising class of compounds effective against rhabdoviruses, which severely impact the aquaculture industry. In this study, we assessed the anti-VHSV activity of umbelliferone (7-hydroxycoumarin) in fathead minnow (FHM) cells and olive flounder Paralichthys olivaceus.

Mining for Metal-Organic Systems: Chemistry Frontiers of Th-, U-, and Zr-Materials.

The conceptual framework presented in this Perspective overviews the design principles of innovative thorium-based materials that could address urgent needs of the medicinal, nuclear energy, and waste remediation sectors from the lens of zirconium and uranium analogs. We survey the intersections of Zr, Th, and U chemistry with a focus on how the intrinsic behavior of each metal translates to broader material properties, including, but not limited to, structural and topological diversity, preferential metal-ligand binding, and reactivity. On the example of several classes of materials, including organometallic complexes, polyoxometalates, and the primary focus of this Perspective, metal-organic frameworks (MOFs), the design principles that govern the preparation of Zr-, Th-, and U-compounds, including oxophilicity, variation in oxidation states, and stable coordination environments have been considered.

Clinical outcomes of colorectal neoplasm with positive resection margin after endoscopic submucosal dissection.

A positive resection margin after colorectal endoscopic submucosal dissection (ESD) is associated with an increased risk of recurrence. We aimed to identify the clinical significance of positive resection margins in colorectal neoplasms after ESD. We reviewed 632 patients who had en bloc colorectal ESD at two hospitals between 2015 and 2020.

Friends or Foes: Fundamental Principles of Th-Organic Scaffold Chemistry Using Zr-Analogs as a Guide.

The fundamental interest in actinide chemistry, particularly for the development of thorium-based materials, is experiencing a renaissance owing to the recent and rapidly growing attention to fuel cycle reactors, radiological daughters for nuclear medicine, and efficient nuclear stockpile development. Herein, we uncover fundamental principles of thorium chemistry on the example of Th-based extended structures such as metal-organic frameworks in comparison with the discrete systems and zirconium extended analogs, demonstrating remarkable over two-and-half-year chemical stability of Th-based frameworks as a function of metal node connectivity, amount of defects, and conformational linker rigidity through comprehensive spectroscopic and crystallographic analysis as well as theoretical modeling. Despite exceptional chemical stability, we report the first example of studies focusing on the reactivity of the most chemically stable Th-based frameworks in comparison with the discrete Th-based systems such as metal-organic complexes and a cage, contrasting multicycle recyclability and selectivity (>97%) of the extended structures in comparison with the molecular compounds.

Breaking the photoswitch speed limit.

The forthcoming generation of materials, including artificial muscles, recyclable and healable systems, photochromic heterogeneous catalysts, or tailorable supercapacitors, relies on the fundamental concept of rapid switching between two or more discrete forms in the solid state. Herein, we report a breakthrough in the "speed limit" of photochromic molecules on the example of sterically-demanding spiropyran derivatives through their integration within solvent-free confined space, allowing for engineering of the photoresponsive moiety environment and tailoring their photoisomerization rates. The presented conceptual approach realized through construction of the spiropyran environment results in ~1000 times switching enhancement even in the solid state compared to its behavior in solution, setting a record in the field of photochromic compounds.

Cytochrome P450 Family 46 Subfamily A Member 1 Promotes the Progression of Colorectal Cancer by Inducing Tumor Cell Proliferation and Angiogenesis.

Background/aim: Cytochrome P450 family 46 subfamily A member 1 (CYP46A1) has been implicated in the development and progression of various cancers. This study aimed to analyze the expression of CYP46A1, examining its relationship with oncogenic behaviors, and determining its prognostic implications in colorectal cancer (CRC).

Materials And Methods: A total of 225 patients with CRC who underwent curative surgical resection were examined using paraffin-embedded tissue blocks and subjected to tumor-specific survival analysis.

Symmetry-Mismatched SBU Transformation in MOFs: Postsynthetic Metal Exchange from Zn to Fe and Its Effects on Gas Adsorption and Dye Selectivity.

This research explores the alteration of metal-organic frameworks (MOFs) using a method called postsynthetic metal exchange. We focus on the shift from a Zn-based MOF containing a [ZnO(COO)] secondary building unit (SBU) of octahedral site symmetry (ANT-1(Zn)) to a Fe-based one with a [FeO(COO)] SBU of trigonal prismatic site symmetry (ANT-1(Fe)). The symmetry-mismatched SBU transformation cleverly maintains the MOF's overall structure by adjusting the conformation of the flexible 1,3,5-benzenetribenzoate linker to alleviate the framework strain.

In-vitro immunomodulatory responses and antiviral activities of antimicrobial peptide octominin against fish pathogenic viruses.

Antimicrobial peptides (AMPs) are considered a novel approach to stimulate fish antiviral mechanisms for defense against a broad range of viral infections by enhancing immunomodulatory activities. Octominin is an AMP derived from the defense proteins of Octopus minor. In this study, preliminary screening of octominin against viral hemorrhagic septicemia virus (VHSV), infectious hematopoietic necrosis virus (IHNV), and infectious pancreatic necrosis virus (IPNV) was carried out.

An antiviral optimized extract from Sanguisorba officinalis L. roots using response surface methodology, and its efficacy in controlling viral hemorrhagic septicemia of olive flounder (Paralichthys olivaceus).

Viral hemorrhagic septicemia causes considerable economic losses for Korea's olive flounder (Paralichthys olivaceus) aquaculture farms; therefore, effective antiviral agents for controlling viral hemorrhagic septicemia virus (VHSV) infection are imperative. The present study implemented a Box-Behnken design and cytopathic reduction assay to derive an optimized extract of Sanguisorba officinalis L. roots (OE-SOR) with maximum antiviral activity against VHSV.

Cooperative and Orthogonal Switching in the Solid State Enabled by Metal-Organic Framework Confinement Leading to a Thermo-Photochromic Platform.

Cooperative behavior and orthogonal responses of two classes of coordinatively integrated photochromic molecules towards distinct external stimuli were demonstrated on the first example of a photo-thermo-responsive hierarchical platform. Synergetic and orthogonal responses to temperature and excitation wavelength are achieved by confining the stimuli-responsive moieties within a metal-organic framework (MOF), leading to the preparation of a novel photo-thermo-responsive spiropyran-diarylethene based material. Synergistic behavior of two photoswitches enables the study of stimuli-responsive resonance energy transfer as well as control of the photoinduced charge transfer processes, milestones required to advance optoelectronics development.

Superprotonic Conductivity of MOFs Confining Zwitterionic Sulfamic Acid as Proton Source and Conducting Medium.

A few metal-organic frameworks (MOFs), which typically use strong acids as proton sources, display superprotonic conductivity (≈10  S cm ); however, they are rare due to the instability of MOFs in highly acidic conditions. For the first time, we report superprotonic conductivity using a moderately acidic guest, zwitterionic sulfamic acid (HSA), which is encapsulated in MOF-808 and MIL-101. HSA acts not only as a proton source but also as a proton-conducting medium due to its extensive hydrogen bonding ability and zwitterion effect.

Metal-Photoswitch Friendship: From Photochromic Complexes to Functional Materials.

Cooperative metal-photoswitch interfaces comprise an application-driven field which is based on strategic coupling of metal cations and organic photochromic molecules to advance the behavior of both components, resulting in dynamic molecular and material properties controlled through external stimuli. In this Perspective, we highlight the ways in which metal-photoswitch interplay can be utilized as a tool to modulate a system's physicochemical properties and performance in a variety of structural motifs, including discrete molecular complexes or cages, as well as periodic structures such as metal-organic frameworks. This Perspective starts with photochromic molecular complexes as the smallest subunit in which metal-photoswitch interactions can occur, and progresses toward functional materials.

Ligand functionalization of defect-engineered Ni-MOF-74.

Incorporating functionality into the framework of metal-organic frameworks (MOFs) has attracted substantial interest because the physical and chemical properties of MOFs can be tuned by functionalizing pores. The ligand functionalization of MOF-74 is challenging because of its pristine organic ligand and framework structure. Herein, we report a series of ligand-functionalized Ni-MOF-74 derivatives synthesized by defect engineering using a mixed-ligand approach.

Confinement-Driven Photophysics in Hydrazone-Based Hierarchical Materials.

Confinement-imposed photophysics was probed for novel stimuli-responsive hydrazone-based compounds demonstrating a conceptual difference in their behavior within 2D versus 3D porous matrices for the first time. The challenges associated with photoswitch isomerization arising from host interactions with photochromic compounds in 2D scaffolds could be overcome in 3D materials. Solution-like photoisomerization rate constants were realized for sterically demanding hydrazone derivatives in the solid state through their coordinative immobilization in 3D scaffolds.

Capture Instead of Release: Defect-Modulated Radionuclide Leaching Kinetics in Metal-Organic Frameworks.

Comparison of defect-controlled leaching-kinetics modulation of metal-organic frameworks (MOFs) and porous functionalized silica-based materials was performed on the example of a radionuclide and radionuclide surrogate for the first time, revealing an unprecedented readsorption phenomenon. On a series of zirconium-based MOFs as model systems, we demonstrated the ability to capture and retain >99% of the transuranic Am radionuclide after 1 week of storage. We report the possibility of tailoring radionuclide release kinetics in MOFs through framework defects as a function of postsynthetically installed organic ligands including cation-chelating crown ether-based linkers.

Spatial distribution modulation of mixed building blocks in metal-organic frameworks.

The placement of mixed building blocks at precise locations in metal-organic frameworks is critical to creating pore environments suitable for advanced applications. Here we show that the spatial distribution of mixed building blocks in metal-organic frameworks can be modulated by exploiting the different temperature sensitivities of the diffusion coefficients and exchange rate constants of the building blocks. By tuning the reaction temperature of the forward linker exchange from one metal-organic framework to another isoreticular metal-organic framework, core-shell microstructural and uniform microstructural metal-organic frameworks are obtained.

Creating Tunable Mesoporosity by Temperature-Driven Localized Crystallite Agglomeration.

A new synthetic approach for tunable mesoporous metal-organic frameworks (MeMs) is developed. In this approach, mesopores are created in the process of heat conversion of highly mosaic metal-organic framework (MOF) crystals with non-interpenetrated low-density nanocrystallites into MOF crystals with two-fold interpenetrated high-density nanocrystallites. The two-fold interpenetration reduces the volume of the nanocrystallites in the mosaic crystal, and the accompanying localized agglomeration of the nanocrystallites results in the formation of mesopores among the localized crystallite agglomerates.

Superprotonic Conductivity of MOF-808 Achieved by Controlling the Binding Mode of Grafted Sulfamate.

A metal-organic framework (MOF) having superprotonic conductivity, MOF-808, is prepared by modulating the binding mode of the sulfamate (SA) moieties grafted onto the metal clusters. The activation of the SA-grafted MOF-808 at 150 °C changes the binding mode of the grafted SA from monodentate to bridging bidentate, thus converting the neutral amido (-S-NH ) moiety of the grafted SA to the more acidic cationic sulfiliminium (-S=NH ) moiety. Further, the acidic sulfiliminium moiety of MOF-808-4SA-150 results in more efficient proton conduction than the amido moiety of MOF-808-4SA-60.

Amine-Tagged Fragmented Ligand Installation for Covalent Modification of MOF-74.

MOF-74 is one of the most explored metal-organic frameworks (MOFs), but its functionalization is limited to the dative post-synthetic modification (PSM) of the monodentate solvent site. Owing to the nature of the organic ligand and framework structure of MOF-74, the covalent PSM of MOF-74 is very demanding. Herein, we report, for the first time, the covalent PSM of amine-tagged defective Ni-MOF-74, which is prepared by de novo solvothermal synthesis by using aminosalicylic acid as a functionalized fragmented organic ligand.

Comparison of antibacterial activity and phenolic constituents of bark, lignum, leaves and fruit of Rhus verniciflua.

Rhus verniciflua is commonly known as a lacquer tree in Korea. The bark of R. verniciflua has been used as an immunostimulator in traditional medicine, but also causes allergic dermatitis due to urushiol derivatives.