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Porous Halogen-Bonded Frameworks Assembled through Hetero-polytopic Ion Pair Templation.
Angew Chem Int Ed Engl
December 2024
Research School of Chemistry, Australian National University, Canberra, ACT, 2601, Australia.
Halogen-bonding (XB) interactions have been extensively studied in the preparation of crystalline frameworks, yet porous 3D framework materials built on XBs remain elusive. The donor-acceptor interactions are strengthened by use of anionic XB acceptors; however, the requisite charge-balancing cations typically disrupt the framework and occupy potential void space. In this work, we prepare a tetratopic XB donor bearing a crown ether moiety for sodium cation sequestration.
View Article and Find Full Text PDFWater-Pore Flow Permeation through Multivalent H-Bonding Pyridine-2,6-dicarboxamide-histamine/Histidine Water Channels.
J Am Chem Soc
December 2024
Adaptive Supramolecular Nanosystems Group, University of Montpellier, Institut Européen des Membranes, ENSCM-CNRS, UMR5635, Place E. Bataillon CC047, Montpellier 34095, France.
Aquaporins (AQPs) are natural proteins that can selectively transport water across cell membranes. Heterogeneous H-bonding of water with the inner wall of the pores of AQPs is of maximal importance regarding the optimal stabilization of water clusters within channels, leading to selective pore flow water transport against ions. To gain deeper insight into the water permeation mechanisms, simpler artificial water channels (AWCs) have been developed.
View Article and Find Full Text PDFPhotocurable Sol-Gel Formulations for the Fabrication of Titanium Carbide/Carbon Nanocomposites via Digital Light Processing.
ACS Appl Mater Interfaces
December 2024
Department of Industrial Engineering, University of Padova, Via Marzolo 9, Padova 35131, Italy.
Additive manufacturing of carbide materials has received significant attention in the past years due to the ability to fabricate complex structures over different length scales. However, the typical limitations for powder-laden inks, such as nozzle clogging, rheological and geometric constraints, particle sedimentation, light-scattering and absorbing phenomena, narrow the range of available processes to manufacture carbide materials via conventional particle-based systems. To address these shortcomings, we have developed a one-pot synthetic route for the preparation of sol-gel-based UV-photocurable formulations, aiming at the fabrication of titanium carbide/carbon nanocomposites using digital light processing printing, pointing to potential applications in the field of nuclear physics.
View Article and Find Full Text PDFSynthesis of Single-Crystal Two-Dimensional Covalent Organic Frameworks and Uncovering Their Hidden Structural Features by Three-Dimensional Electron Diffraction.
J Am Chem Soc
December 2024
Department of Chemistry, Faculty of Science, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore.
Two-dimensional covalent organic frameworks (2D COFs) are formed by the polycondensation of geometrically specific monomers to grow covalently connected 2D polygonal polymers over the - plane and supramolecular polymerization and/or crystallization of 2D sheets along the direction to constitute layer architectures. Despite various efforts, the synthesis of single-crystal 2D COFs remains a challenging goal. Here, we report the synthesis of single-crystal 2D COFs, by taking the representative imine-linked TPB-DMTP-COF as an example, to reveal the key synthetic parameters that control the crystallization of 2D COFs.
View Article and Find Full Text PDFSpace Exploration of Metal-Organic Frameworks in the Mesopore Regime.
Acc Chem Res
December 2024
Key Laboratory of Biomedical Polymers, Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China.
ConspectusThe past decades have witnessed the proliferation of porous materials offering high surface areas and the revolution in gas storage and separation, where metal-organic frameworks (MOFs) stand out as an important family. Alongside the pursuit of higher surface area, the increase in the size of guests, such as nanoparticles and biomolecules, has also led to the demand for larger space defined by the pores and cages within the MOF structure, from the conventional micropore regime (<2 nm) toward the mesopore regime (2-50 nm). Among the essential elements in the design of MOFs, molecular building blocks, their coordination and spatial arrangement, the chemistry for molecular design, and coordination bonds have become relatively mature, offering precise control of the shape and environment of the molecularly defined 3D cages; however, the correlation between the geometrical parameters and the size of polyhedrons describing the cages, concerning the spatial arrangement of building blocks, is much less explored.
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