Self-Assembly of a Triazolylferrocenyl Dendrimer in Water Yields Nontraditional Intrinsic Green Fluorescent Vesosomes for Nanotheranostic Applications

Author(s)

Perli, Gabriel ^{[1, 2]} ; Wang, Qi ^{[3, 4]} ; Braga, Carolyne B. ^[1] ; Bertuzzi, Diego L. ^[1] ; Fontana, Liniquer A. ^[1] ; Soares, Marco C. P. ^[5] ; Ruiz, Jaime ^[3] ; Megiatto, Jr., Jackson D. ^[1] ; Astruc, Didier ^[3] ; Ornelas, Catia ^[1]

Affiliation

^[1] Univ Estadual Campinas, Inst Chem, Rua Josue Castro, Cidade Univ Zeferino Vaz, BR-13083970 Campinas, SP - Brazil

^[2] Univ Lyon, Ingenierie Mat Polymeres, INSA Lyon, CNRS UMR 5233, F-69621 Villeurbanne - France

^[3] Univ Bordeaux, ISM, UMR CNRS 5255, F-33405 Talence - France

^[4] Anhui Univ, Inst Phys Sci & Informat Technol, Hefei 230601 - Peoples R China

^[5] Univ Estadual Campinas, Sch Mech Engn, Lab Photon Mat & Devices, Rua Mendeleyev 200, Cidade Univ Zeferino Vaz, BR-13083860 Campinas, SP - Brazil

• Document type: Journal article
• Source: Journal of the American Chemical Society; v. 143, n. 33, p. 12948-12954, AUG 25 2021.
• Web of Science Citations: 0

Abstract

The promising field of nanomedicine stimulates a continuous search for multifunctional nanotheranostic systems for imaging and drug delivery. Herein, we demonstrate that application of supramolecular chemistry's concepts in dendritic assemblies can enable the formation of advanced dendrimer-based nanotheranostic devices. A dendrimer bearing 81 triazolylferrocenyl terminal groups adopts a more compact shell-like structure in polar solvents with the ferrocenyl peripheral groups backfolding toward the hydrophobic dendrimer interior, while exposing the more polar triazole moieties as the dendritic shell. Akin to lipids, the compact dendritic structure self-assembles into uniform nanovesicles that in turn self-assemble into larger vesosomes in water. The vesosomes emit green nontraditional intrinsic fluorescence (NTIL), which is an emerging property as there are no classical fluorophores in the dendritic macromolecular structure. This work confirms the hypothesis that the NTIL emission is greatly enhanced by rigidification of the supramolecular assemblies containing heteroatomic subluminophores (HASLs) and by the presence of electron rich functional groups on the periphery of dendrimers. This work is the first one detecting NTIL in ferrocenyl-terminated dendrimers. Moreover, the vesosomes are stable in biological medium, are uptaken by cells, and show cytotoxic activity against cancer cells. Accordingly, the self-organization of these dendrimers into tertiary structures promotes the emergence of new properties enabling the same component, in this case, ferrocenyl group, to function as both antitumoral drug and fluorophore. (AU)

• FAPESP's process: 18/02093-0 - Development of new nanomaterials for nanomedicine applications
• Grantee: Cátia Cristina Capêlo Ornelas Megiatto
• Support Opportunities: Regular Research Grants
• FAPESP's process: 13/22160-0 - Development of original synthetic strategies for the preparation of supramolecular Interlocked polymers
• Grantee: Jackson Dirceu Megiatto Junior
• Support Opportunities: Research Grants - Young Investigators Grants
• FAPESP's process: 21/00555-9 - Development of polymeric nanoparticles and multifunctional dendrimers for drug delivery
• Grantee: Igor Dias Jurberg
• Support Opportunities: Regular Research Grants
• FAPESP's process: 17/06146-8 - Development of nanocarriers based on dendrimers and polymer nanoparticles for selective delivery of goniothalamin, piplartine and Monastrol
• Grantee: Carolyne Brustolin Braga
• Support Opportunities: Scholarships in Brazil - Post-Doctoral