Person: Rubio Retama, Benito Jorge
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First Name
Benito Jorge
Last Name
Rubio Retama
Affiliation
Universidad Complutense de Madrid
Faculty / Institute
Farmacia
Department
Química en Ciencias Farmacéuticas
Area
Química Física
Identifiers
7 results
Search Results
Now showing 1 - 7 of 7
Item Exploring the Origin of the Thermal Sensitivity of Near-Infrared-II Emitting Rare Earth Nanoparticles(Applied Materials and Interfaces, 2023) Hamraoui, Khouloud; Torres Vera, Vivian Andrea; Zabala Gutiérrez, Irene; Casillas Rubio, Alejandro; Alqudwa Fattouh, Mohammed; Benayas, Antonio; Marín, Riccardo; Natile, Marta María; Manso Silván, Miguel; Rubio Zuazo, Juan; Jaque, Daniel; Melle Hernández, Sonia; Gómez Calderón, Óscar; Rubio Retama, Benito JorgeRare-earth doped nanoparticles (RENPs) are attracting increasing interest in materials science due to their optical, magnetic, and chemical properties. RENPs can emit and absorb radiation in the second biological window (NIR-II, 1000-1400 nm) making them ideal optical probes for photoluminescence (PL) in vivo imaging. Their narrow emission bands and long PL lifetimes enable autofluorescence-free multiplexed imaging. Furthermore, the strong temperature dependence of the PL properties of some of these RENPs makes remote thermal imaging possible. This is the case of neodymium and ytterbium co-doped NPs that have been used as thermal reporters for in vivo diagnosis of, for instance, inflammatory processes. However, the lack of knowledge about how the chemical composition and architecture of these NPs influence their thermal sensitivity impedes further optimization. To shed light on this, we have systematically studied their emission intensity, PL decay time curves, absolute PL quantum yield, and thermal sensitivity as a function of the core chemical composition and size, active-shell, and outer-inert-shell thicknesses. The results revealed the crucial contribution of each of these factors in optimizing the NP thermal sensitivity. An optimal active shell thickness of around 2 nm and an outer inert shell of 3.5 nm maximize the PL lifetime and the thermal response of the NPs due to the competition between the temperature-dependent back energy transfer, the surface quenching effects, and the confinement of active ions in a thin layer. These findings pave the way for a rational design of RENPs with optimal thermal sensitivity.Item Boosting the Near-Infrared Emission of Ag2S Nanoparticles by a Controllable Surface Treatment for Bioimaging Applications(ACS Applied Materials & Interfaces, 2022) Zabala Gutiérrez, Irene; Gerke, Christoph; Shen, Yingli; Ximendes, Erving Clayton; Manso Silvan, Miguel; Marin, Riccardo; Jaque García, Daniel; Gómez Calderón, Óscar; Melle Hernández, Sonia; Rubio Retama, Benito JorgeAg2S nanoparticles are the staple for high-resolution preclinical imaging and sensing owing to their photochemical stability, low toxicity, and photoluminescence (PL) in the second near-infrared biological window. Unfortunately, Ag2S nanoparticles exhibit a low PL efficiency attributed to their defective surface chemistry, which curbs their translation into the clinics. To address this shortcoming, we present a simple methodology that allows to improve the PL quantum yield from 2 to 10%, which is accompanied by a PL lifetime lengthening from 0.7 to 3.8 μs. Elemental mapping and X-ray photoelectron spectroscopy indicate that the PL enhancement is related to the partial removal of sulfur atoms from the nanoparticle’s surface, reducing surface traps responsible for nonradiative de-excitation processes. This interpretation is further backed by theoretical modeling. The acquired knowledge about the nanoparticles’ surface chemistry is used to optimize the procedure to transfer the nanoparticles into aqueous media, obtaining water-dispersible Ag2S nanoparticles that maintain excellent PL properties. Finally, we compare the performance of these nanoparticles with other near-infrared luminescent probes in a set of in vitro and in vivo experiments, which demonstrates not only their cytocompatibility but also their superb optical properties when they are used in vivo, affording higher resolution images.Item 10-Fold Quantum Yield Improvement of Ag2S Nanoparticles by Fine Compositional Tuning(ACS Applied materials and interfaces, 2020) Ortega Rodríguez, Alicia; Shen, Yingli; Zabala Gutiérrez, Irene; Santos, Harrison D. A.; Torres Vera, Vivian Andrea; Ximedes, Erving; Villaverde Cantizano, Gonzalo; Lifante, José; Gerke, Christoph; Fernández Monsalve, Nuria; Gómez Calderón, Óscar; Melle Hernández, Sonia; Marqués Hueso, José; Méndez González, Diego; Laurenti, Marco; Jones, Callum M. S.; López Romero, Juan Manuel; Contreras Cáceres, Rafael; Jaque García, Daniel; Rubio Retama, Benito Jorge; Garma Pons, SantiagoAg2S semiconductor nanoparticles (NPs) are near-infrared luminescent probes with outstanding properties (good biocompatibility, optimum spectral operation range, and easy biofunctionalization) that make them ideal probes for in vivo imaging. Ag2S NPs have, indeed, made possible amazing challenges including in vivo brain imaging and advanced diagnosis of the cardiovascular system. Despite the continuous redesign of synthesis routes, the emission quantum yield (QY) of Ag2S NPs is typically below 0.2%. This leads to a low luminescent brightness that avoids their translation into the clinics. In this work, an innovative synthetic methodology that permits a 10-fold increment in the absolute QY from 0.2 up to 2.3% is presented. Such an increment in the QY is accompanied by an enlargement of photoluminescence lifetimes from 184 to 1200 ns. The optimized synthetic route presented here is based on a fine control over both the Ag core and the Ag/S ratio within the NPs. Such control reduces the density of structural defects and decreases the nonradiative pathways. In addition, we demonstrate that the superior performance of the Ag2S NPs allows for high-contrast in vivo bioimaging. .Item A brighter era for silver chalcogenide semiconductor nanocrystals(Optical Materials, 2023) Ming, Liyan; Zabala Gutiérrez, Irene; Gómez Calderón, Óscar; Melle Hernández, Sonia; Ximendes , Erwing; Rubio Retama, Benito Jorge; Marín, RiccardoSilver chalcogenide semiconductor nanocrystals (Ag2E SNCs) have become a household name in the biomedical field, where they are used as contrast agents in bioimaging, photothermal therapy agents, and luminescent nanothermometers. The prominent position they have come to occupy in this field stems from a unique combination of features, above all near-infrared excitation and emission alongside low cytotoxicity. However, the first reports on Ag2E SNCs showed that a great limitation of these luminescent nanomaterials resided in their low photoluminescence quantum yield, which results in reduced brightness: a crippling feature in bioimaging and biosensing. In this article, we provide an overview of the strategies developed to overcome this hurdle. These strategies aim to remedy the presence of defects in the SNC core and/or surface, the presence of metallic silver, and off-stoichiometric composition. These features stem from the high mobility and redox potential of Ag+ ions, alongside the difficulty in controlling the nucleation and growth rate of Ag2E SNCs. The effectiveness of each approach is discussed. Lastly, a perspective on future research efforts to make Ag2E SNCs even brighter – and thus more effective in biomedical applications – is provided, with the hope of inspiring further investigation on these nanomaterials with a rich, complex set of physicochemical and spectroscopic properties.Item Contribution of resonance energy transfer to the luminescence quenching of upconversion nanoparticles with graphene oxide(Journal of Colloid and Interface Science, 2020) Méndez González, Diego; Gómez Calderón, Óscar; Melle Hernández, Sonia; González Izquierdo, Jesús; Bañares Morcillo, Luis; López Díaz, David; Velazquez Salicio, M. Mercedes; López Cabarcos, Enrique; Rubio Retama, Benito Jorge; Laurenti, MarcoUpconversion nanoparticles (UCNP) are increasingly used due to their advantages over conventional fluorophores, and their use as resonance energy transfer (RET) donors has permitted their application as biosensors when they are combined with appropriate RET acceptors such as graphene oxide (GO). However, there is a lack of knowledge about the design and influence that GO composition produces over the quenching of these nanoparticles that in turn will define their performance as sensors. In this work, we have analysed the total quenching efficiency, as well as the actual values corresponding to the RET process between UCNPs and GO sheets with three different chemical compositions. Our findings indicate that excitation and emission absorption by GO sheets are the major contributor to the observed luminescence quenching in these systems. This challenges the general assumption that UCNPs luminescence deactivation by GO is caused by RET. Furthermore, RET efficiency has been theoretically calculated by means of a semiclassical model considering the different nonradiative energy transfer rates from each Er3+ ion to the GO thin film. These theoretical results highlight the relevance of the relative positions of the Er3+ ions inside the UCNP with respect to the GO sheet in order to explain the RET-induced efficiency measurements.Item The effects of dopant concentration and excitation intensity on the upconversion and downconversion emission processes of β-NaYF4:Yb3+,Er3+nanoparticles(Journal of materials chemistry C, 2021) Torres Vera, Vivian Andrea; Méndez González, Diego; Ramos Ramos, D. J.; Igalla El-Youssfi, Asmae; Laurenti, Marco; Contreras Cáceres, Rafael; López Cabarcos, Enrique; Díaz García, Elena; Rubio Retama, Benito Jorge; Melle Hernández, Sonia; Gómez Calderón, ÓscarThe dopant concentration of lanthanide ions in photon upconversion nanoparticles (UCNPs) remains one of the key points to boost the brightness of these nanomaterials and, therefore, their application developments. Here, we analyzed the effect of Er3+ and Yb3+ dopant concentrations of b-NaYF4:Yb3+,Er3+ nanoparticles on the visible upconversion and near-infrared downconversion luminescence intensities. Our approach carefully excluded all other factors whose variation affects luminescence properties such as the size, morphology, crystal structure, ion distribution, ligand, and surrounding medium, allowing us to exactly infer the influence of the ratio of Yb3+ to Er3+ ions on the nanoparticle luminescence. To maintain the size and morphological properties of nanoparticles, we used a total dopant concentration of 22% while varying the ratio of Yb3+ to Er3+ ions from 0 to 10. A huge increase in luminescence takes place as the Yb/Er ratio increases following a power-law behavior, and this luminescence enhancement is greater at low excitation intensities. Above a Yb/Er ratio of around two, saturation occurs with a slight peak when this ratio is around four. Simulations using a rate equation model showed that upconversion luminescence (UCL) is mainly produced by the energy transfer between neighboring Er3+ ions at low Yb/Er ratios, while at high ratios, the energy transfer from Yb3+ to Er3+ ions dominates. However, downconversion luminescence (DCL) is produced at all analyzed ratios, except 0, by the previous mechanism.Item Ion-induced bias in Ag2S luminescent nanothermometers(Nanoscale, 2023) París Ogayar, Marina; Méndez González, Diego; Zabala Gutiérrez, Irene; Artiga , Alvaro; Rubio Retama, Benito Jorge; Gómez Calderón, Óscar; Melle Hernández, Sonia; Alda Serrano, Javier; Espinosa, Ana; Jaque, Daniel; Marín Viadel, RicardoLuminescence nanothermometry allows measuring temperature remotely and in a minimally invasive way by using the luminescence signal provided by nanosized materials. This technology has allowed, for example, the determination of intracellular temperature and in vivo monitoring of thermal processes in animal models. However, in the biomedical context, this sensing technology is crippled by the presence of bias (cross-sensitivity) that reduces the reliability of the thermal readout. Bias occurs when the impact of environmental conditions different from temperature also modifies the luminescence of the nanothermometers. Several sources that cause loss of reliability have been identified, mostly related to spectral distortions due to interaction between photons and biological tissues. In this work, we unveil an unexpected source of bias induced by metal ions. Specifically, we demonstrate that the reliability of Ag2S nanothermometers is compromised during the monitoring of photothermal processes produced by iron oxide nanoparticles. The observed bias occurs due to the heat-induced release of iron ions, which interact with the surface of the Ag2S nanothermometers, enhancing their emission. The results herein reported raise a warning to the community working on luminescence nanothermometry, since they reveal that the possible sources of bias in complex biological environments, rich in molecules and ions, are more numerous than previously expected.