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In vitro upconverting/downshifting luminescent detection of tumor markers based on Eu3+-activated core-shell-shell lanthanide nanoprobes.

ABSTRACT: Trivalent europium (Eu3+) doped inorganic nanoparticles (NPs), emerging as a new class of red luminescent nanoprobes, have shown great promise in bioapplications as diverse as luminescent bioassays and disease theranostics owing to their superior optical properties such as long-lived downshifting luminescence (DSL) and upconverting luminescence (UCL). However, the exploration of Eu3+-doped NPs as red luminescent bioprobes particularly combined with DSL and UCL of Eu3+ hitherto remains untouched. Herein, we report a rational core-shell-shell (CSS) design strategy to construct Eu3+-activated NaGdF4:Yb/Tm@NaGdF4:Eu@NaEuF4 CSS NPs functionalized with efficient UCL and dissolution-enhanced DSL of Eu3+ for in vitro tumor marker detection and tumor-targeted imaging. By utilizing the CSS NPs as red luminescent nanoprobes, we demonstrate the successful UCL and DSL bioassays of a typical hepatic carcinoma biomarker, alpha-fetoprotein (AFP), in human serum samples. The UCL bioassay shows a limit of detection (LOD) of AFP down to 20 pg mL-1 (290 fM), which is the lowest among luminescent bioassays of AFP ever reported, and a 30-fold improvement relative to that of the commercial dissociation-enhanced lanthanide fluoroimmunoassay kit. Meanwhile the DSL bioassay, by employing the identical CSS NPs, can serve as a self-referential validation for the reliability and accuracy of the UCL bioassay for AFP detection. Furthermore, these CSS NPs can also function well in tumor-targeted UCL bioimaging, thereby revealing the great promise of the designed CSS NPs as red luminescent bioprobes in ultrasensitive in vitro detection of tumor markers in clinical diagnosis.

SUBMITTER: Liu Y

PROVIDER: S-EPMC6018526 | biostudies-literature | 2016 Aug

REPOSITORIES: biostudies-literature

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In vitro upconverting/downshifting luminescent detection of tumor markers based on Eu3+-activated core-shell-shell lanthanide nanoprobes.

Liu Yongsheng Y Zhou Shanyong S Zhuo Zhu Z Li Renfu R Chen Zhuo Z Hong Maochun M Chen Xueyuan X

Chemical science 20160512 8

Trivalent europium (Eu3+) doped inorganic nanoparticles (NPs), emerging as a new class of red luminescent nanoprobes, have shown great promise in bioapplications as diverse as luminescent bioassays and disease theranostics owing to their superior optical properties such as long-lived downshifting luminescence (DSL) and upconverting luminescence (UCL). However, the exploration of Eu3+-doped NPs as red luminescent bioprobes particularly combined with DSL and UCL of Eu3+< ...[more]

PMID: 30155152

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Project description:A family of homodinuclear Ln3+ (Ln3+ = Gd3+, Eu3+) luminescent complexes with the general formula [Ln2(β-diketonato)6(N-oxide)y] has been developed to study the effect of the β-diketonato and N-oxide ligands on their thermometric properties. The investigated complexes are [Ln2(tta)6(pyrzMO)2] (Ln = Eu (1·C7H8), Gd (5)), [Ln2(dbm)6(pyrzMO)2] (Ln = Eu (2), Gd (6)), [Ln2(bta)6(pyrzMO)2] (Ln = Eu (3), Gd (7)), [Ln2(hfac)6(pyrzMO)3] (Ln = Eu (4), Gd (8)) (pyrzMO = pyrazine N-oxide, Htta = thenoyltrifluoroacetone, Hdbm = dibenzoylmethane, Hbta = benzoyltrifluoroacetone, Hhfac = hexafluoroacetylacetone, C7H8 = toluene), and their 4,4'-bipyridine N-oxide (bipyMO) analogues. Europium complexes emit a bright red light under UV radiation at room temperature, whose intensity displays a strong temperature (T) dependence between 223 and 373 K. This remarkable variation is exploited to develop a series of luminescent thermometers by using the integrated intensity of the 5D0 → 7F2 europium transition as the thermometric parameter (Δ). The effect of different β-diketonato and N-oxide ligands is investigated with particular regard to the shape of thermometer calibration (Δ vs T) and relative thermal sensitivity curves: i.e.. the change in Δ per degree of temperature variation usually indicated as Sr (% K-1). The thermometric properties are determined by the presence of two nonradiative deactivation channels, back energy transfer (BEnT) from Eu3+ to the ligand triplet levels and ligand to metal charge transfer (LMCT). In the complexes bearing tta and dbm ligands, whose triplet energy is ca. 20000 cm-1, both deactivation channels are active in the same temperature range, and both contribute to determine the thermometric properties. Conversely, with bta and hfac ligands the response of the europium luminescence to temperature variation is ruled by LMCT channels since the high triplet energy (>21400 cm-1) makes BEnT ineffective in the investigated temperature range.

Dataset Information

In vitro upconverting/downshifting luminescent detection of tumor markers based on Eu3+-activated core-shell-shell lanthanide nanoprobes.

Publications

<i>In vitro</i> upconverting/downshifting luminescent detection of tumor markers based on Eu<sup>3+</sup>-activated core-shell-shell lanthanide nanoprobes.

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