7 research outputs found
Modulating the catalytic activity of enzyme-like nanoparticles through their surface functionalization
The inclusion of transition metal catalysts into nanoparticle scaffolds permits the creation of catalytic nanosystems (nanozymes) able to imitate the behaviour of natural enzymes. Here we report the fabrication of a family of nanozymes comprised of bioorthogonal ruthenium catalysts inserted in the protective monolayer of gold nanoparticles. By introducing simple modifications to the functional groups at the surface of the nanozymes, we have demonstrated control over the kinetic mechanism of our system. Cationic nanozymes with hydrophobic surface functionalities tend to replicate the classical Michaelis Menten model, while those with polar groups display substrate inhibition behaviour, a key mechanism present in 20% of natural enzymes. The structural parameters described herein can be used for creating artificial nanosystems that mimic the complexity observed in cell machinery. © 2018 The Royal Society of Chemistry
Janus Gold Nanostars-Mesoporous Silica Nanoparticles for NIR-Light-Triggered Drug Delivery
"This is the peer reviewed version of the following article: Hernández Montoto, Andy, Antoni Llopis-Lorente, Mónica Gorbe, José M. Terrés, Roberto Cao Milán, Borja Díaz de Greñu, María Alfonso, et al. 2019. Janus Gold Nanostars Mesoporous Silica Nanoparticles for NIR-Light-Triggered Drug Delivery. Chemistry A European Journal 25 (36). Wiley: 8471 78. doi:10.1002/chem.201900750, which has been published in final form at https://doi.org/10.1002/chem.201900750. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving."[EN] Janus gold nanostar-mesoporous silica nanoparticle (AuNSt-MSNP) nanodevices able to release an entrapped payload upon irradiation with near infrared (NIR) light were prepared and characterized. The AuNSt surface was functionalized with a thiolated photolabile molecule (5), whereas the mesoporous silica face was loaded with a model drug (doxorubicin) and capped with proton-responsive benzimidazole-beta-cyclodextrin supramolecular gatekeepers (N 1). Upon irradiation with NIR-light, the photolabile compound 5 photodissociated, resulting in the formation of succinic acid, which induced the opening of the gatekeeper and cargo delivery. In the overall mechanism, the gold surface acts as a photochemical transducer capable of transforming the NIR-light input into a chemical messenger (succinic acid) that opens the supramolecular nanovalve. The prepared hybrid nanoparticles were non-cytotoxic to HeLa cells, until they were irradiated with a NIR laser, which led to intracellular doxorubicin release and hyperthermia. This induced a remarkable reduction in HeLa cells viability.The authors gratefully acknowledge financial support from the Spanish Government [Projects MAT2015-64139-C4-1-R, AGL2015-70235-C2-2-R and SAF2017-84689-R (MINECO/AEI/FEDER, UE)], the Generalitat Valenciana (Project PROMETEO2018/024) and European Union (Erasmus Mundus Programme, Action 2, grant agreement number 2014-0870/001001). A.H. thanks the Erasmus Mundus Programme for his PhD scholarship through the EuroInkaNet project. A.L.-L. thanks "La Caixa" Banking Foundation for his PhD scholarship.Hernández-Montoto, A.; Llopis-Lorente, A.; Gorbe, M.; Terrés-Haro, JM.; Cao Milán, R.; Díaz De Greñu-Puertas, B.; Alfonso-Navarro, M.... (2019). Janus Gold Nanostars-Mesoporous Silica Nanoparticles for NIR-Light-Triggered Drug Delivery. Chemistry - A European Journal. 25(36):8471-8478. https://doi.org/10.1002/chem.201900750S847184782536Yang, P., Gai, S., & Lin, J. (2012). Functionalized mesoporous silica materials for controlled drug delivery. Chemical Society Reviews, 41(9), 3679. doi:10.1039/c2cs15308dSancenón, F., Pascual, L., Oroval, M., Aznar, E., & Martínez-Máñez, R. (2015). Gated Silica Mesoporous Materials in Sensing Applications. ChemistryOpen, 4(4), 418-437. doi:10.1002/open.201500053Giménez, C., Climent, E., Aznar, E., Martínez-Máñez, R., Sancenón, F., Marcos, M. D., … Rurack, K. (2014). Towards Chemical Communication between Gated Nanoparticles. Angewandte Chemie International Edition, n/a-n/a. doi:10.1002/anie.201405580Giménez, C., Climent, E., Aznar, E., Martínez-Máñez, R., Sancenón, F., Marcos, M. D., … Rurack, K. (2014). Über den chemischen Informationsaustausch zwischen gesteuerten Nanopartikeln. Angewandte Chemie, 126(46), 12838-12843. doi:10.1002/ange.201405580Llopis-Lorente, A., Díez, P., Sánchez, A., Marcos, M. D., Sancenón, F., Martínez-Ruiz, P., … Martínez-Máñez, R. (2017). Interactive models of communication at the nanoscale using nanoparticles that talk to one another. Nature Communications, 8(1). doi:10.1038/ncomms15511Song, N., & Yang, Y.-W. (2015). Molecular and supramolecular switches on mesoporous silica nanoparticles. Chemical Society Reviews, 44(11), 3474-3504. doi:10.1039/c5cs00243eAznar, E., Oroval, M., Pascual, L., Murguía, J. R., Martínez-Máñez, R., & Sancenón, F. (2016). Gated Materials for On-Command Release of Guest Molecules. Chemical Reviews, 116(2), 561-718. doi:10.1021/acs.chemrev.5b00456Koutsopoulos, S. (2012). Molecular fabrications of smart nanobiomaterials and applications in personalized medicine. Advanced Drug Delivery Reviews, 64(13), 1459-1476. doi:10.1016/j.addr.2012.08.002Bao, G., Mitragotri, S., & Tong, S. (2013). Multifunctional Nanoparticles for Drug Delivery and Molecular Imaging. Annual Review of Biomedical Engineering, 15(1), 253-282. doi:10.1146/annurev-bioeng-071812-152409Hernández Montoto, A., Montes, R., Samadi, A., Gorbe, M., Terrés, J. M., Cao-Milán, R., … Martínez-Máñez, R. (2018). Gold Nanostars Coated with Mesoporous Silica Are Effective and Nontoxic Photothermal Agents Capable of Gate Keeping and Laser-Induced Drug Release. ACS Applied Materials & Interfaces, 10(33), 27644-27656. doi:10.1021/acsami.8b08395De la Torre, C., Domínguez-Berrocal, L., Murguía, J. R., Marcos, M. D., Martínez-Máñez, R., Bravo, J., & Sancenón, F. (2018). ϵ
-Polylysine-Capped Mesoporous Silica Nanoparticles as Carrier of the C
9h
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Vertical assembly of few-layer graphene decorated with iron oxide nanoparticles on gold surfaces
Modulating the Catalytic Activity of Enzyme-like Nanoparticles Through their Surface Functionalization.
The inclusion of transition metal catalysts into nanoparticle scaffolds permits the creation of catalytic nanosystems (nanozymes) able to imitate the behaviour of natural enzymes. Here we report the fabrication of a family of nanozymes comprised of bioorthogonal ruthenium catalysts inserted in the protective monolayer of gold nanoparticles. By introducing simple modifications to the functional groups at the surface of the nanozymes, we have demonstrated control over the kinetic mechanism of our system. Cationic nanozymes with hydrophobic surface functionalities tend to replicate the classical Michaelis Menten model, while those with polar groups display substrate inhibition behaviour, a key mechanism present in 20 % of natural enzymes. The structural parameters described herein can be used for creating artificial nanosystems that mimic the complexity observed in cell machinery