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
6 results
Search Results
Now showing 1 - 6 of 6
Item Thermoresponsive Polymeric Nanolenses Magnify the Thermal Sensitivity of Single Upconverting Nanoparticles(Small, 2022) Lu, Dasheng; Rubio Retama, Benito Jorge; Marin, Riccardo; Marqués Ponce, Manuel Ignacio; Gómez Calderón, Óscar; Melle Hernández, Sonia; Haro González, Patricia; Jaque García, Daniel; Bandrés Ponce, Francisco JavierLanthanide-based upconverting nanoparticles (UCNPs) are trustworthy workhorses in luminescent nanothermometry. The use of UCNPs-based nanothermometers has enabled the determination of the thermal properties of cell membranes and monitoring of in vivo thermal therapies in real time. However, UCNPs boast low thermal sensitivity and brightness, which, along with the difficulty in controlling individual UCNP remotely, make them less than ideal nanothermometers at the single-particle level. In this work, it is shown how these problems can be elegantly solved using a thermoresponsive polymeric coating. Upon decorating the surface of NaYF4 :Er3+ ,Yb3+ UCNPs with poly(N-isopropylacrylamide) (PNIPAM), a >10-fold enhancement in optical forces is observed, allowing stable trapping and manipulation of a single UCNP in the physiological temperature range (20-45 °C). This optical force improvement is accompanied by a significant enhancement of the thermal sensitivity- a maximum value of 8% °C+1 at 32 °C induced by the collapse of PNIPAM. Numerical simulations reveal that the enhancement in thermal sensitivity mainly stems from the high-refractive-index polymeric coating that behaves as a nanolens of high numerical aperture. The results in this work demonstrate how UCNP nanothermometers can be further improved by an adequate surface decoration and open a new avenue toward highly sensitive single-particle nanothermometry.Item Reaching Deeper: Absolute In Vivo Thermal Reading of Liver by Combining Superbright Ag2S Nanothermometers and In Silico Simulations(Advanced Science, 2021) Lifante Cañavate, José; Shen, Yingli; Zabala Gutiérrez, Irene; Rubia Rodríguez, Irene; Ortega, Daniel; Fernández Monsalve, Nuria; Melle Hernández, Sonia; Granado García, Miriam; Rubio Retama, Benito Jorge; Jaque García, Daniel; Ximendes, Erving ClaytonLuminescent nano‐thermometry is a fast‐developing technique with great potential for in vivo sensing, diagnosis, and therapy. Unfortunately, it presents serious limitations. The luminescence generated by nanothermometers, from which thermal readout is obtained, is strongly distorted by the attenuation induced by tissues. Such distortions lead to low signal levels and entangle absolute and reliable thermal monitoring of internal organs. Overcoming both limitations requires the use of high‐brightness luminescent nanothermometers and adopting more complex approaches for temperature estimation. In this work, it is demonstrated how superbright Ag2S nanothermometers can provide in vivo, reliable, and absolute thermal reading of the liver during laser‐induced hyperthermia. For that, a new procedure is designed in which thermal readout is obtained from the combination of in vivo transient thermometry measurements and in silico simulations. The synergy between in vivo and in silico measurements has made it possible to assess relevant numbers such as the efficiency of hyperthermia processes, the total heat energy deposited in the liver, and the relative contribution of Ag2S nanoparticles to liver heating. This work provides a new way for absolute thermal sensing of internal organs with potential application not only to hyperthermia processes but also to advanced diagnosis and therapy.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 Control of upconversion luminescence by gold nanoparticle size: from quenching to enhancement(Nanoscale, 2019) Méndez González, Diego; Melle Hernández, Sonia; Gómez Calderón, Óscar; Laurenti, Marco; Cabrera Granado, Eduardo; Egatz-Gómez, Ana; López Cabarcos, Enrique; Rubio Retama, Benito Jorge; Díaz García, ElenaMetallic nanostructures have the potential to modify the anti-Stokes emission of upconverting nanoparticles (UCNPs) by coupling their plasmon resonance with either the excitation or the emission wavelength of the UCNPs. In this regard gold nanoparticles (AuNPs) have often been used in sensors for UCNP luminescence quenching or enhancement, although systematic studies are still needed in order to design optimal UCNP–AuNP based biosensors. Amidst mixed experimental evidence of quenching or enhancement, two key factors arise: the nanoparticle distance and nanoparticle size. In this work, we synthesize AuNPs of different sizes to assess their influence on the luminescence of UCNPs. We find that strong luminescence quenching due to resonance energy transfer is preferentially achieved for small AuNPs, peaking at an optimal size. A further increase in the AuNP size is accompanied by a reduction of luminescence quenching due to an incipient plasmonic enhancement effect. This enhancement counterbalances the luminescence quenching effect at the biggest tested AuNP size. The experimental findings are theoretically validated by studying the decay rate of the UCNP emitters near a gold nanoparticle using both a classical phenomenological model and the finite-difference time-domain method. Results from this study establish general guidelines to consider when designing sensors based on UCNPs–AuNPs as donor–quencher pairs, and suggest the potential of plasmon-induced luminescence enhancement as a sensing strategy.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.Item Ultrafast photochemistry produces superbright short-wave infrared dots for low-dose in vivo imaging(Nature communications, 2020) Santos, Harrison D. A.; Zabala Gutiérrez, Irene; Shen, Yingli; Lifante, José; Ximendes, Erving; Laurenti, Marco; Méndez González, Diego; Melle Hernández, Sonia; Gómez Calderón, Óscar; López Cabarcos, Enrique; Fernández Monsalve, Nuria; Chavez Coria, Irene; Lucena Agell, Daniel; Monge, Luis; Mackenzie, Mark D.; Marqués Hueso, José; Jones, Callum M. S.; Jacinto, Carlos; Rosal, Blanca, del; Kar, Ajoy K.; Rubio Retama, Benito Jorge; Jaque García, DanielOptical probes operating in the second near-infrared window (NIR-II, 1,000-1,700 nm), where tissues are highly transparent, have expanded the applicability of fluorescence in the biomedical field. NIR-II fluorescence enables deep-tissue imaging with micrometric resolution in animal models, but is limited by the low brightness of NIR-II probes, which prevents imaging at low excitation intensities and fluorophore concentrations. Here, we present a new generation of probes (Ag2S superdots) derived from chemically synthesized Ag2S dots, on which a protective shell is grown by femtosecond laser irradiation. This shell reduces the structural defects, causing an 80-fold enhancement of the quantum yield. PEGylated Ag2S superdots enable deep-tissue in vivo imaging at low excitation intensities (<10 mW cm−2) and doses (<0.5 mg kg−1), emerging as unrivaled contrast agents for NIR-II preclinical bioimaging. These results establish an approach for developing superbright NIR-II contrast agents based on the synergy between chemical synthesis and ultrafast laser processing.