Spectroscopic research of upconversion nanomaterials based on complex oxide compounds doped with rare-earth ion pairs: Benefit for cancer diagnostics by upconversion fluorescence and radio sensitive methods/Spektroskopische Untersuchung von mit Ionenpaaren Seltener Erden dotierten Upconversion-Nanokompositen: Nutzen für die Krebsdiagnostik durch Upconversion-Fluoreszenz und strahlungssensitive Methoden

Anastasia V. Ryabova; Daria V. Pominova; Victoria A. Krut’ko; Maria G. Komova; Victor B. Loschenov

doi:10.1515/plm-2013-0013

Article

Spectroscopic research of upconversion nanomaterials based on complex oxide compounds doped with rare-earth ion pairs: Benefit for cancer diagnostics by upconversion fluorescence and radio sensitive methods/Spektroskopische Untersuchung von mit Ionenpaaren Seltener Erden dotierten Upconversion-Nanokompositen: Nutzen für die Krebsdiagnostik durch Upconversion-Fluoreszenz und strahlungssensitive Methoden

Anastasia V. Ryabova , Daria V. Pominova , Victoria A. Krut’ko , Maria G. Komova and Victor B. Loschenov

Published/Copyright: April 11, 2013

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From the journal Photonics & Lasers in Medicine Volume 2 Issue 2

Abstract

Background: Highly photochemically stable nanoparticles, in which upconversion luminescence can be excited – so-called upconversion nanocrystals (UC-NCs) – exhibit widely separated (up to 500 nm) narrow luminescence bands in the visible (VIS) region located far from the excitation near-infrared (NIR) laser radiation, and thus can be more easily identified compared to organic luminophores and semiconductor nanoparticles. Due to a deep penetration of exciting infrared (IR) radiation, the absence of parasitic fluorescence of biomolecules and the absence of phototoxicity and photobleaching upon near IR excitation, UC-NCs can be efficiently used as fluorescent probes in biological studies and fluorescence diagnostics (FD). The doping of such nanoparticles with Gd³⁺ ions provides the additional possibility of combining fluorescence visualization with magnetic resonance imaging, which will considerably improve the sensitivity of diagnostics of cancer tumors even in the early stages.

Materials and methods: We studied the upconversion characteristics of inorganic nanoparticles made of different materials doped with rare-earth ion (REI) pairs Yb³⁺-Er³⁺ and Yb³⁺-Tm³⁺ as functions of the concentration and composition of a dopant at different excitation intensities. Matrices chosen for doping were complex polycrystalline oxide rare earth compounds Gd₂GeMoO₈, La₄Gd₁₀B₆Ge₂O₃₄, and Gd₁₁SiP₃O₂₆ which permit the introduction of significant concentrations of the activator luminescence ions (Yb³⁺, Er³⁺ and Tm³⁺), synthesized by solid-phase reaction methods from corresponding oxides. The final product was obtained by combined precipitation of initial components from aqueous solutions followed by the annealing of hydroxide mixtures and grinding. The redistribution of the intensity of the 550 nm ²H_11/2, ⁴S_3/2→⁴I_15/2 and 650 nm ⁴F_9/2→⁴I_15/2 upconversion luminescence bands in Er³⁺ was investigated depending on matrices, dopants, and the laser power density. The quantum yield and lifetime of upconversion luminescence were determined for individual electronic transitions, which were used to optimize the composition of dopants in matrices.

Results: Based on the results obtained, the matrix La₄Gd₁₀B₆Ge₂O₃₄ is most effective for the upconversion process in the VIS spectrum. Doping nanoparticles by REI pairs Yb³⁺-Er³⁺ and Yb³⁺-Tm³⁺, each has its advantages. REI pair Yb³⁺-Er³⁺ is good for energy transfer in the green and/or red part of the spectrum as well as for the FD and can be used for a further energy transfer to the photosensitizers at photodynamic therapy (PDT). REI pair Yb³⁺-Tm³⁺ transform the infrared radiation in the blue region of the spectrum, which is also suitable for FD and PDT and additional intensive energy conversion in NIR will allow for deep tissue imaging.

Conclusion: The investigated complex polycrystalline oxide compounds are promising as diagnostic agents for biological tissues visualization by fluorescence, light scattering, and nuclear magnetic resonance imaging.

Zusammenfassung

Hintergrund: Photochemisch hochstabile Nanopartikel, in denen Upconversion-Lumineszenz angeregt werden kann – die sogenannten Upconversion-Nanokomposite (UC-NCs) – weisen eng begrenzte, schmale Lumineszenz-Banden (bis 500 nm) im sichtbaren Wellenlängenbereich auf, die weit genug von der Anregungs-Laserstrahlung im Nahinfrarot (NIR)-Bereich entfernt sind und somit leichter gegenüber organischen Luminophoren und Halbleiternanopartikeln zu identifizieren sind. Durch die hohe Eindringtiefe des infraroten (IR) Anregungslichtes und das Fehlen parasitärer Fluoreszenz durch Biomoleküle sowie Phototoxizitäts- und Photobleechingeffekte im Bereich der IR-Anregung können UC-NCs effizient als Fluoreszenzsonden für biologische Untersuchungen und die Fluoreszenzdiagnostik (FD) eingesetzt werden. Die Dotierung solcher Nanopartikel mit Gd³⁺-Ionen bietet zusätzlich die Möglichkeit der Kombination von Fluoreszenz-Visualisierung und Magnetresonanz-Bildgebung, was die Empfindlichkeit der Diagnostik von Tumoren auch in frühen Stadien deutlich verbessert.

Material und Methoden: Wir untersuchten die Upconversion-Eigenschaften von anorganischen Nanopartikeln aus unterschiedlichen Materialien, die mit Ionenpaaren Seltener Erden dotiert wurden (Yb³⁺-Er³⁺ und Yb³⁺-Tm³⁺), und zwar in Abhängigkeit von der Konzentration und Zusammensetzung des Dotands bei unterschiedlichen Anregungsenergien. Als Grundsubstanzen für eine Dotierung wurden komplexe polykristalline Oxidverbindungen Seltener Erden ausgewählt (Gd₂GeMoO₈, La₄Gd₁₀ B₆Ge₂O₃₄, und Gd₁₁SiP₃O₂₆), die die Einführung signifikanter Konzentrationen der Aktivator-Lumineszenz-Ionen (Yb³⁺, Er³⁺ und Tm³⁺) gestatten – synthetisiert durch Festphasenreaktionsmethoden aus korrespondierenden Oxiden. Das Endprodukt wurde durch die kombinierte Ausfällung der anfänglichen Komponenten aus wässriger Lösung und anschließendes Glühen und Mahlen der Hydroxidgemische erzeugt. Die Umverteilung der Intensität der 550 nm ²H_11/2, ⁴S_3/2→⁴I_15/2 und 650 nm ⁴F_9/2→⁴I_15/2 Upconversion-Lumineszenz-Banden wurde in Abhängigkeit von den Grundstoffen, Dotanden und der Laserleistungsdichte untersucht. Die Quantenausbeute und die Lebensdauer der Upconversion-Lumineszenz wurden für einzelne elektronische Übergänge bestimmt, die zur Optimierung der Dotanden-Zusammensetzung verwendet wurden.

Ergebnisse: Wie sich zeigte, ist die La₄Gd₁₀B₆Ge₂O₃₄-Matrix im sichtbaren Spektralbereich am effektivsten für den Upconversion-Prozess. Beide dotierenden Ionenpaare Seltener Erden (Yb³⁺-Er³⁺ und Yb³⁺-Tm³⁺) haben ihre Vorteile. Das Yb³⁺-Er³⁺-Ionenpaar ist gut für die Energieübertragung im grünen und/oder roten Spektralbereich als auch für die FD und kann für eine weitere Energieübertragung auf den Photosensibilisator während der photodynamischen Therapie (PDT) verwendet werden. Das Yb³⁺-Tm³⁺-Ionenpaar verwandelt die IR-Strahlung im blauen Bereich des Spektrums, was ebenfalls für die FD und PDT geeignet ist und eine zusätzliche intensive Energieumwandlung in NIR bewirkt, was ein Imaging tiefer Gewebeschichten erlaubt.

Fazit: Die untersuchten komplexen polykristallinen Oxidverbindungen sind als diagnostische Mittel zur Darstellung biologischen Gewebes mittels Fluoreszenz, Lichtstreuung und Magnetresonanz-Bildgebung geeignet.

Keywords: upconversion; nanocrystals; complex oxide REE compounds; quantum yield; spectroscopy; deep infrared excitation; fluorescence; Upconversion; Nanokomposite; Quantenausbeute; Spektroskopie; tiefe Infrarot-Anregung; Fluoreszenz

Corresponding author: Anastasia V. Ryabova, Prokhorov General Physics Institute, Russian Academy of Sciences, Vavilova 38, Moscow, 119991, Russian Federation

This work was supported by a grant from the President of the Russian Federation (Project No. MK-4408.2011.2) and by the Russian Foundation for Basic Research (grants No. 12-02-12080-ofi-m, No. 11-08-01322-a).

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Received: 2013-2-1

Revised: 2013-3-7

Accepted: 2013-3-9

Published Online: 2013-4-11

Published in Print: 2013-5-1

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https://doi.org/10.1515/plm-2013-0013

Keywords for this article

upconversion; nanocrystals; complex oxide REE compounds; quantum yield; spectroscopy; deep infrared excitation; fluorescence; Upconversion; Nanokomposite; Quantenausbeute; Spektroskopie; tiefe Infrarot-Anregung; Fluoreszenz