Enormous attention has been paid to upconverted circularly polarized luminescence (UC-CPL). However, so far, chiral species are still needed in UC-CPL materials, either through the covalent or noncovalent bond. Here, we report a general supramolecular coassembly approach for the fabrication of UC-CPL systems from completely achiral components. We have found that an achiral -symmetric molecule could form a chiral nanohelix through symmetry breaking, which could serve as a general helical platform to endow achiral guests with induced chirality and CPL activity. Two different photon upconversion systems, namely, triplet-triplet annihilation photon upconversion (TTA-UC) donor/acceptor pairs and inorganic lanthanide upconversion nanoparticles (UCNPs), are selected. When these two systems coassembled with the chiral nanohelix made from an achiral -symmetric molecule, hybrid nanohelix structures formed and UC-CPL activity was induced. Through such an approach, we demonstrated that the fabrication of the UC-CPL materials does not require any chiral molecules. Moreover, we have shown that the polarization of UC-CPL can be tuned by the helicity of the nanohelix, which could be controlled through the seeded vortex. Our work provides a general approach for designing tunable UC-CPL materials from completely achiral motifs, which largely expands the research scope of the CPL materials.
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http://dx.doi.org/10.1021/acsnano.0c08539 | DOI Listing |
Chemistry
November 2024
Department of Chemistry, State Key Lab of Molecular Engineering of Polymers, Shanghai Key Lab of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai, China.
The absolute and relative configurations of a macrocyclic natural product bearing multiple chirality have a crucial influence on its physical and biological properties. Nevertheless, their preparation with full stereocontrol remains largely unexplored in synthetic community. Here, we show a stereodivergent macrocyclization under dynamic chiral confinement in which the stepwise chirality switching of a chiral space directs complete stereocontrol.
View Article and Find Full Text PDFACS Appl Mater Interfaces
November 2024
Department of Chemistry, UGC Centre of Advance Study-II, Guru Nanak Dev University, Amritsar143005, Punjab , India.
The building block has been designed and synthesized, which exhibits different achiral morphologies in good solvents, forming nanospheres in THF and nanoflowers in 1,4-dioxane. In the presence of water as a poor cosolvent, demonstrates an agnostic behavior, generating left-handed superhelices in the water:THF (80:20) solvent system. However, when the good solvent is switched to 1,4-dioxane, a change in chirality is observed in the water:1,4-dioxane (30:70) solvent system, resulting in the formation of fused nanospheres.
View Article and Find Full Text PDFJ Am Chem Soc
September 2024
Department of Chemistry, University of Texas at Austin, 105 E 24th St., Austin, Texas 78712, United States.
The first total synthesis of the pentacyclic phenylnaphthacenoid type II polyketide antibiotic formicamycin H is described. A key feature of the synthesis involves the convergent, regioselective assembly of the tetracyclic core via ruthenium-catalyzed α-ketol-benzocyclobutenone [4 + 2] cycloaddition. Double dehydration of the diol-containing cycloadduct provides an achiral enone, which upon asymmetric nucleophilic epoxidation and further manipulations delivers the penultimate tetracyclic trichloride in enantiomerically enriched form.
View Article and Find Full Text PDFJ Chromatogr A
November 2024
Institute of Medicinal Biotechnology, Peking Union Medical College & Chinese Academy of Medical Sciences, Tian Tan Xi Li No.2, Beijing 100050, PR China. Electronic address:
Simultaneous separation of compounds with multiple chiral centers and highly similar structures presents significant challenges. This study developed a novel supercritical fluid chromatography (SFC) method with reduced organic solvent consumption and robust separation capabilities to address these challenges. The method was applied to simultaneously achieve enantioselective, diastereoselective, and achiral separation of palonosetron hydrochloride and its six impurities.
View Article and Find Full Text PDFNature
October 2024
Department of Industrial Chemistry 'Toso Montanari', University of Bologna, Bologna, Italy.
Photoenzymes are light-powered biocatalysts that typically rely on the excitation of cofactors or unnatural amino acids for their catalytic activities. A notable natural example is the fatty acid photodecarboxylase, which uses light energy to convert aliphatic carboxylic acids to achiral hydrocarbons. Here we report a method for the design of a non-natural photodecarboxylase based on the excitation of enzyme-bound catalytic intermediates, rather than reliance on cofactor excitation.
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