Person:
Zabala Gutiérrez, Irene

First Name

Irene

Last Name

Zabala Gutiérrez

URI

https://hdl.handle.net/20.500.14352/86286

Affiliation

Universidad Complutense de Madrid

Faculty / Institute

Farmacia

Department

Química en Ciencias Farmacéuticas

Identifiers

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Now showing 1 - 10 of 12

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, Jorge; Jaque García, Daniel; Ximendes, Erving Clayton
Luminescent 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.
Upconverting Nanoparticles in Aqueous Media: Not a Dead-End Road. Avoiding Degradation by Using Hydrophobic Polymer Shells
(Small, 2021) Méndez González, Diego; Torres Vera, Vivian Andrea; Zabala Gutiérrez, Irene; Gerke, Christoph; Cascales Sedano, Concepción; Rubio Retama, Jorge; Gómez Calderón, Óscar; Melle Hernández, Sonia; Laurenti, Marco
The stunning optical properties of upconverting nanoparticles (UCNPs) have inspired promising biomedical technologies. Nevertheless, their transfer to aqueous media is often accompanied by intense luminescence quenching, partial dissolution by water, and even complete degradation by molecules such as phosphates. Currently, these are major issues hampering the translation of UCNPs to the clinic. In this work, a strategy is developed to coat and protect β-NaYF4 UCNPs against these effects, by growing a hydrophobic polymer shell (HPS) through miniemulsion polymerization of styrene (St), or St and methyl methacrylate mixtures. This allows one to obtain single core@shell UCNPs@HPS with a final diameter of ≈60–70 nm. Stability studies reveal that these HPSs serve as a very effective barrier, impeding polar molecules to affect UCNPs optical properties. Even more, it allows UCNPs to withstand aggressive conditions such as high dilutions (5 μg mL−1), high phosphate concentrations (100 mm), and high temperatures (70 °C). The physicochemical characterizations prove the potential of HPSs to overcome the current limitations of UCNPs. This strategy, which can be applied to other nanomaterials with similar limitations, paves the way toward more stable and reliable UCNPs with applications in life sciences.
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 Jorge
Rare-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.
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 Jorge
Ag2S 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.
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, Santiago
Ag2S 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. .
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, Riccardo
Silver 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.
Electrospraying as a Technique for the Controlled Synthesis of Biocompatible PLGA@Ag2S and PLGA@Ag2S@SPION Nanocarriers with Drug Release Capability
(Pharmaceutics, 2022) Alvear Jiménez, Alexis; Zabala Gutiérrez, Irene; Shen, Yingli; Villaverde Cantizano, Gonzalo; Lozano Chamizo, Laura; Guardia, Pablo; Tinoco Rivas, Miguel; García Pinel, Beatriz; Prados, José; Melguizo, Consolación; López Romero, Manuel; Jaque, Daniel; Filice, Marco; Contreras Cáceres, Rafael
Project number: 74
Las TICs: un instrumento de ayuda en las prácticas de laboratorio
(2022) Laurenti, Marco; Ovejero Paredes, Karina; Zabala Gutiérrez, Irene; Sanchez Sanche, Visitación; Yusta San Roman, Piedad; Contreras Cáceres, Rafael; Filice, Marco; López Cabarcos, Enrique; Marciello, Marzia; Méndez González, Diego; Rubio Retama, Benito Jorge; Villaverde Cantizano, Gonzalo
Desde la implantación del Espacio Europeo de Educación Superior nos encontramos ante dos grandes retos; el desarrollo metodológico y tecnológico en la formación y docencia on-line y en segundo lugar la cada vez más elevada especialización requerida a los estudiantes durante el Grado y Doble Grado en Farmacia. Esto hace que el foco de la formación de los estudiantes se desvíe de los conocimientos básicos y competencias de formación tanto en el trabajo experimental como en el conocimiento teórico. El proyecto se encuadra en el marco de la asignatura obligatoria Física Aplicada a Farmacia de Grado y Doble Grado en Farmacia, unas carreras con una elevada carga práctica y experimental.
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, Ricardo
Luminescence 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.
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, Jorge; Jaque García, Daniel
Optical 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.