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Herein we address the question of whether a supramolecular finite metal-organic structure such as a cage or metal-organic polyhedron (MOP) can be synthesized via controlled cleavage of a three-dimensional (3D) metal-organic structure. To demonstrate this, we report the synthesis of a Cu(II)-based cuboctahedral MOP through orthogonal olefinic bond cleavage of the cavities of a 3D, Cu(II)-based, metal-organic framework (MOF). Additionally, we demonstrate that controlling the ozonolysis conditions used for the cleavage enables Clip-off Chemistry synthesis of two cuboctahedral MOPs that differ by their external functionalization: one in which all 24 external groups represent a mixture of aldehydes, carboxylic acids, acetals and esters, and one in which all are aldehydes.
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http://dx.doi.org/10.1021/jacs.4c09431 | DOI Listing |
Chem Commun (Camb)
September 2025
INSA Rouen Normandie, Univ Rouen Normandie, Univ Caen Normandie, ENSICAEN, CNRS, Institut CARMeN (UMR 6064), F-76000 Rouen, France.
While synthetic developments for the synthesis of trifluoromethoxylated arenes have flourished over the years, the cleavage of a C-OCF bond remains a niche topic and a synthetic challenge to overcome. This review provides an overview of major advances made in activating a strong aryl C-OCF bond, enabling C-C, C-H, and C-Heteroatom bond formations. These advances underscore the transformative potential of further developments in this emerging field.
View Article and Find Full Text PDFOrg Biomol Chem
September 2025
Universidad de Córdoba, Grupo de Química Computacional, Facultad de Ciencias Básicas, Carrera 6, No. 77-305, Montería-Córdoba, Colombia.
This study explores the photochemical conversion of BN-Dewar benzene into BN-benzvalene derivatives, offering a strategic route to heteroatom-containing valence isomers with distinctive electronic properties. Using time-dependent density functional theory (TD-DFT) and electron localization function (ELF) analyses, the excited-state mechanism and associated structural rearrangements were elucidated. Vertical excitation to the S state was found to weaken the CC and B-N bonds while strengthening the N-Si bond in silyl-substituted derivatives, a key factor enabling efficient BN-benzvalene formation.
View Article and Find Full Text PDFNucleic Acids Res
September 2025
Department of Biological Sciences, Columbia University, New York, NY 10027, United States.
The 3'-end cleavage and polyadenylation of pre-mRNAs is dependent on a key hexanucleotide motif known as the polyadenylation signal (PAS). The PAS hexamer is recognized by the mammalian polyadenylation specificity factor (mPSF). AAUAAA is the most frequent PAS hexamer and together with AUUAAA, the second most frequent hexamer, account for ∼75% of the poly(A) signals.
View Article and Find Full Text PDFEnviron Pollut
September 2025
State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012, China; Key Laboratory of Groundwater Pollution Simulation and Control Ministry of Ecology and Environment, Chinese Research Academy of Environmental Sciences, Beiji
Paddy soil represents a critical sink for microplastics (MPs), where frequent redox oscillations from wet-dry alternation can accelerate MPs aging, and alter dissolved organic matter (DOM) composition in paddy soil. However, this process remains poorly understood to date. Here, we systematically investigated the aging of three MPs and their structural effects on DOM in paddy soil during wet-dry alternation.
View Article and Find Full Text PDFJ Org Chem
September 2025
Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources (Ministry of Education of China), Guangxi Key Laboratory of Chemistry and Molecular Engineering of Medicinal Resources, University Engineering Research Center for Chemistry of Characteristic Medicinal Resources (Guangxi),
Herein, we have developed a Brønsted acid catalyzed 1,5-migration of functional groups from indole-tethered ynamides to prepare a variety of 2-acyltryptamines in good to excellent yields with high site-selectivity at the C2-position of indoles. Mechanistic studies revealed that the reaction underwent an intramolecular cyclization, 1,2-migration of the vinyl group, and C-N bond cleavage by hydrolysis in a one pot. The reaction features broad substrate scope, good functional group compatibility, 1,5-migration of functional groups, C-N bond cleavage to form C-C bond, and diverse 2-acyltryptamine scaffolds.
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