Carlos Alarcón-Fernández, Carlos Zaldo, Manuel Bañobre-López, Juan Gallo, Pedro Ramos-Cabrer, Sandra Plaza-García, Gonzalo Villaverde, Alejandro Ruperti, Concepción Cascales
{"title":"用于多模态MRI对比、近红外成像和高灵敏度红外发光比例测温的生物相容性NaLn(WO4)2核壳纳米血小板。","authors":"Carlos Alarcón-Fernández, Carlos Zaldo, Manuel Bañobre-López, Juan Gallo, Pedro Ramos-Cabrer, Sandra Plaza-García, Gonzalo Villaverde, Alejandro Ruperti, Concepción Cascales","doi":"10.1039/d5tb00548e","DOIUrl":null,"url":null,"abstract":"<p><p>Multifunctional nanoprobes combining magnetic resonance imaging (MRI) contrast as well as near infrared (NIR) imaging and thermometry are demonstrated by using quasi-bidimensional core-multishell nanostructures based on the scheelite-like NaLn(WO<sub>4</sub>)<sub>2</sub> host (Ln = trivalent lanthanide). These nanostructures are composed of a NaHo(WO<sub>4</sub>)<sub>2</sub> core, plus a first shell of Tm,Yb:NaGd(WO<sub>4</sub>)<sub>2</sub>, and a second shell of Nd,Yb:NaGd(WO<sub>4</sub>)<sub>2</sub>. Proton nuclear magnetic relaxation dispersion studies and MRI of water dispersions of nanoprobes, whose quasi-bidimensional geometries promote the interaction of Gd<sup>3+</sup> with water protons, reveal behaviors evolving from a <i>T</i><sub>1</sub>-weighted MR contrast agent (CA) at 1.5 T to a highly effective <i>T</i><sub>2</sub>-weighted MR CA at ultrahigh magnetic fields of 7 T and above, and even a dual <i>T</i><sub>1</sub>/<i>T</i><sub>2</sub>-weighted CA at a clinical 3 T magnetic field. By NIR excitation (<i>λ</i><sub>EXC</sub> ∼ 803 nm) of Nd<sup>3+</sup>, luminescence-based thermometry was accomplished at wavelengths within the second biological transparency window (II-BW) through ratiometric analysis of <sup>4</sup>F<sub>3/2</sub> → <sup>4</sup>I<sub>11/2</sub> Nd<sup>3+</sup> (<i>λ</i> = 1058 nm) and <sup>2</sup>F<sub>5/2</sub> → <sup>2</sup>F<sub>7/2</sub> Yb<sup>3+</sup> (<i>λ</i> = 996 nm) emissions. Under a biologically safe excitation of 0.68 W cm<sup>-2</sup>, a chemically stable 2 mg mL<sup>-1</sup> nanoprobe water dispersion presents absolute, <i>S</i><sub>A</sub>, and relative, <i>S</i><sub>R</sub>, thermal sensitivities as remarkable as <i>S</i><sub>A</sub> = 480 × 10<sup>-4</sup> K<sup>-1</sup>, and <i>S</i><sub>R</sub> = 0.89% K<sup>-1</sup> at 40 °C (313 K), and temperature resolution <i>δ</i> ≈ 0.1 K. Moreover, through efficient Nd<sup>3+</sup> → Yb<sup>3+</sup> → Tm<sup>3+</sup> and Nd<sup>3+</sup> → Yb<sup>3+</sup> → Ho<sup>3+</sup> energy transfers, NIR photoluminescence from Tm<sup>3+</sup> at ∼1800 nm and Ho<sup>3+</sup> at ∼2000 nm facilitates in depth imaging. The low nanoprobe cytotoxicity allows NIR biolabeling during cellular temperature measurement.</p>","PeriodicalId":94089,"journal":{"name":"Journal of materials chemistry. B","volume":" ","pages":"9642-9665"},"PeriodicalIF":5.7000,"publicationDate":"2025-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Biocompatible NaLn(WO<sub>4</sub>)<sub>2</sub> core-shell nanoplatelets for multimodal MRI contrast, NIR imaging, and high sensitivity infrared luminescent ratiometric thermometry.\",\"authors\":\"Carlos Alarcón-Fernández, Carlos Zaldo, Manuel Bañobre-López, Juan Gallo, Pedro Ramos-Cabrer, Sandra Plaza-García, Gonzalo Villaverde, Alejandro Ruperti, Concepción Cascales\",\"doi\":\"10.1039/d5tb00548e\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>Multifunctional nanoprobes combining magnetic resonance imaging (MRI) contrast as well as near infrared (NIR) imaging and thermometry are demonstrated by using quasi-bidimensional core-multishell nanostructures based on the scheelite-like NaLn(WO<sub>4</sub>)<sub>2</sub> host (Ln = trivalent lanthanide). These nanostructures are composed of a NaHo(WO<sub>4</sub>)<sub>2</sub> core, plus a first shell of Tm,Yb:NaGd(WO<sub>4</sub>)<sub>2</sub>, and a second shell of Nd,Yb:NaGd(WO<sub>4</sub>)<sub>2</sub>. Proton nuclear magnetic relaxation dispersion studies and MRI of water dispersions of nanoprobes, whose quasi-bidimensional geometries promote the interaction of Gd<sup>3+</sup> with water protons, reveal behaviors evolving from a <i>T</i><sub>1</sub>-weighted MR contrast agent (CA) at 1.5 T to a highly effective <i>T</i><sub>2</sub>-weighted MR CA at ultrahigh magnetic fields of 7 T and above, and even a dual <i>T</i><sub>1</sub>/<i>T</i><sub>2</sub>-weighted CA at a clinical 3 T magnetic field. By NIR excitation (<i>λ</i><sub>EXC</sub> ∼ 803 nm) of Nd<sup>3+</sup>, luminescence-based thermometry was accomplished at wavelengths within the second biological transparency window (II-BW) through ratiometric analysis of <sup>4</sup>F<sub>3/2</sub> → <sup>4</sup>I<sub>11/2</sub> Nd<sup>3+</sup> (<i>λ</i> = 1058 nm) and <sup>2</sup>F<sub>5/2</sub> → <sup>2</sup>F<sub>7/2</sub> Yb<sup>3+</sup> (<i>λ</i> = 996 nm) emissions. Under a biologically safe excitation of 0.68 W cm<sup>-2</sup>, a chemically stable 2 mg mL<sup>-1</sup> nanoprobe water dispersion presents absolute, <i>S</i><sub>A</sub>, and relative, <i>S</i><sub>R</sub>, thermal sensitivities as remarkable as <i>S</i><sub>A</sub> = 480 × 10<sup>-4</sup> K<sup>-1</sup>, and <i>S</i><sub>R</sub> = 0.89% K<sup>-1</sup> at 40 °C (313 K), and temperature resolution <i>δ</i> ≈ 0.1 K. Moreover, through efficient Nd<sup>3+</sup> → Yb<sup>3+</sup> → Tm<sup>3+</sup> and Nd<sup>3+</sup> → Yb<sup>3+</sup> → Ho<sup>3+</sup> energy transfers, NIR photoluminescence from Tm<sup>3+</sup> at ∼1800 nm and Ho<sup>3+</sup> at ∼2000 nm facilitates in depth imaging. The low nanoprobe cytotoxicity allows NIR biolabeling during cellular temperature measurement.</p>\",\"PeriodicalId\":94089,\"journal\":{\"name\":\"Journal of materials chemistry. B\",\"volume\":\" \",\"pages\":\"9642-9665\"},\"PeriodicalIF\":5.7000,\"publicationDate\":\"2025-08-06\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of materials chemistry. B\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.1039/d5tb00548e\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of materials chemistry. B","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1039/d5tb00548e","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
Biocompatible NaLn(WO4)2 core-shell nanoplatelets for multimodal MRI contrast, NIR imaging, and high sensitivity infrared luminescent ratiometric thermometry.
Multifunctional nanoprobes combining magnetic resonance imaging (MRI) contrast as well as near infrared (NIR) imaging and thermometry are demonstrated by using quasi-bidimensional core-multishell nanostructures based on the scheelite-like NaLn(WO4)2 host (Ln = trivalent lanthanide). These nanostructures are composed of a NaHo(WO4)2 core, plus a first shell of Tm,Yb:NaGd(WO4)2, and a second shell of Nd,Yb:NaGd(WO4)2. Proton nuclear magnetic relaxation dispersion studies and MRI of water dispersions of nanoprobes, whose quasi-bidimensional geometries promote the interaction of Gd3+ with water protons, reveal behaviors evolving from a T1-weighted MR contrast agent (CA) at 1.5 T to a highly effective T2-weighted MR CA at ultrahigh magnetic fields of 7 T and above, and even a dual T1/T2-weighted CA at a clinical 3 T magnetic field. By NIR excitation (λEXC ∼ 803 nm) of Nd3+, luminescence-based thermometry was accomplished at wavelengths within the second biological transparency window (II-BW) through ratiometric analysis of 4F3/2 → 4I11/2 Nd3+ (λ = 1058 nm) and 2F5/2 → 2F7/2 Yb3+ (λ = 996 nm) emissions. Under a biologically safe excitation of 0.68 W cm-2, a chemically stable 2 mg mL-1 nanoprobe water dispersion presents absolute, SA, and relative, SR, thermal sensitivities as remarkable as SA = 480 × 10-4 K-1, and SR = 0.89% K-1 at 40 °C (313 K), and temperature resolution δ ≈ 0.1 K. Moreover, through efficient Nd3+ → Yb3+ → Tm3+ and Nd3+ → Yb3+ → Ho3+ energy transfers, NIR photoluminescence from Tm3+ at ∼1800 nm and Ho3+ at ∼2000 nm facilitates in depth imaging. The low nanoprobe cytotoxicity allows NIR biolabeling during cellular temperature measurement.