Fully Water-Soluble Polyphosphorhydrazone-Based Radical Dendrimers Functionalized with Tyr-PROXYL Radicals as Metal-Free MRI T1 Contrast Agents

The finding of alternative imaging probes to Gadolinium (Gd) and other metal based contrast agents (CA) is crucial to overcome their established toxicity. Herein we describe the synthesis and characterization of an entirely organic metal-free magnetic resonance imaging (MRI) contrast agent based on...

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Detalles Bibliográficos
Autores: Pinto, Luiz Fernando, Lloveras, Vega, Zhang, Songbai, Liko, Flonja, Veciana, Jaume, Muñoz Gómez, José L, Vidal Gancedo, José
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2020
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/200282
Acceso en línea:http://hdl.handle.net/10261/200282
Access Level:acceso abierto
Palabra clave:Radical dendrimers
Magnetic resonance imaging MRI
Contrast agents
Electron paramagnetic resonance EPR
Organic radicals
Descripción
Sumario:The finding of alternative imaging probes to Gadolinium (Gd) and other metal based contrast agents (CA) is crucial to overcome their established toxicity. Herein we describe the synthesis and characterization of an entirely organic metal-free magnetic resonance imaging (MRI) contrast agent based on polyphosphorhydrazone (PPH) dendrimers, fully functionalized with up to 48 organic nitroxide radical units. We propose an innovative synthetic procedure based on the use of an amino acid linker (Tyr) coupled to each dendrimer′s branch that permits the anchoring of the radicals and at the same time makes possible the control over their water solubility. We demonstrate that the negatively charged resulting PPH GnTyr-PROXYL (n = 0−3) radical dendrimers are excellent candidates to be used as MRI contrast agents, suited for biomedical applications as they show high water solubility, no aggregation problems, and low cytotoxicity, as well as good stability in highly reducing environments. It is achieved a remarkable r1 relaxivity, ca. four times higher (13 mM−1 s −1 ) than the gold-standard Gd-DTPA used in clinics. Furthermore, the r1 and r2 relaxivity per unit of radical showed an increase with the increase in generation of dendrimers.