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

被引:23
作者
Perli, Gabriel [2 ,3 ]
Wang, Qi [1 ,4 ]
Braga, Carolyne B. [2 ]
Bertuzzi, Diego L. [2 ]
Fontana, Liniquer A. [2 ]
Soares, Marco C. P. [5 ]
Ruiz, Jaime [1 ]
Megiatto, Jackson D., Jr. [2 ]
Astruc, Didier [1 ]
Ornelas, Catia [2 ]
机构
[1] Univ Bordeaux, ISM, UMR CNRS 5255, F-33405 Talence, France
[2] Univ Estadual Campinas, Inst Chem, Rua Josue Castro,Cidade Univ Zeferino Vaz, BR-13083970 Campinas, SP, Brazil
[3] Univ Lyon, Ingenierie Mat Polymeres, INSA Lyon, CNRS UMR 5233, F-69621 Villeurbanne, 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
基金
巴西圣保罗研究基金会;
关键词
JANUS DENDRIMERS; CHEMISTRY; DENDRONS; DESIGN; NUMBER; ATOMS; SIZE;
D O I
10.1021/jacs.1c05551
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
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.
引用
收藏
页码:12948 / 12954
页数:7
相关论文
共 46 条
[1]   Supramolecular structures from dendrons and dendrimers [J].
Al-Jamal, KT ;
Ramaswamy, C ;
Florence, AT .
ADVANCED DRUG DELIVERY REVIEWS, 2005, 57 (15) :2238-2270
[2]   Solubilisation and transformation of amphipathic lipidic dendron vesicles (dendrisomes) into mixed micelles [J].
Al-Jamal, KT ;
Sakthivel, T ;
Florence, AT .
COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS, 2005, 268 (1-3) :52-59
[3]   Control over the Redox Cooperative Mechanism of Radical Carbene Transfer Reactions for the Efficient Active-Metal-Template Synthesis of [2]Rotaxanes [J].
Alcantara, Arthur F. P. ;
Fontana, Liniquer A. ;
Almeida, Marlon P. ;
Rigolin, Vitor H. ;
Ribeiro, Marcos A. ;
Barros, Wdeson P. ;
Megiatto, Jackson D., Jr. .
CHEMISTRY-A EUROPEAN JOURNAL, 2020, 26 (35) :7808-7822
[4]   A new method for the synthesis of β-cyano substituted porphyrins and their use as sensitizers in photoelectrochemical devices [J].
Antoniuk-Pablant, A. ;
Terazono, Y. ;
Brennan, B. J. ;
Sherman, B. D. ;
Megiatto, J. D., Jr. ;
Brudvig, G. W. ;
Moore, A. L. ;
Moore, T. A. ;
Gust, D. .
JOURNAL OF MATERIALS CHEMISTRY A, 2016, 4 (08) :2976-2985
[5]   Why is Ferrocene so Exceptional? [J].
Astruc, Didier .
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2017, (01) :6-29
[6]   Dendrimers Designed for Functions: From Physical, Photophysical, and Supramolecular Properties to Applications in Sensing, Catalysis, Molecular Electronics, Photonics, and Nanomedicine [J].
Astruc, Didier ;
Boisselier, Elodie ;
Ornelas, Catia .
CHEMICAL REVIEWS, 2010, 110 (04) :1857-1959
[7]   Soft Nanohydrogels Based on Laponite Nanodiscs: A Versatile Drug Delivery Platform for Theranostics and Drug Cocktails [J].
Becher, Tiago B. ;
Mendonca, Monique C. P. ;
de Farias, Marcelo A. ;
Portugal, Rodrigo, V ;
de Jesus, Marcelo B. ;
Ornelas, Catia .
ACS APPLIED MATERIALS & INTERFACES, 2018, 10 (26) :21891-21900
[8]   Synthesis, characterization, and anticancer activity of folate γ-ferrocenyl conjugatest [J].
Bertuzzi, Diego L. ;
Perli, Gabriel ;
Braga, Carolyne B. ;
Ornelas, Catia .
NEW JOURNAL OF CHEMISTRY, 2020, 44 (12) :4694-4703
[9]   Dendrimers for drug delivery [J].
Caminade, Anne-Marie ;
Turrin, Cedric-Olivier .
JOURNAL OF MATERIALS CHEMISTRY B, 2014, 2 (26) :4055-4066
[10]   Self-Assembly of Photoresponsive Molecular Amphiphiles in Aqueous Media [J].
Chen, Shaoyu ;
Costil, Romain ;
Leung, Franco King-Chi ;
Feringa, Ben L. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2021, 60 (21) :11604-11627