Aqueous synthesis of Ag and Mn co-doped In2S3/ZnS quantum dots with tunable emission for dual-modal targeted imaging

Pei Yu Lai; Chih Ching Huang; Tzung Han Chou; Keng-Liang Ou; Jia Yaw Chang

doi:10.1016/j.actbio.2016.12.028

Aqueous synthesis of Ag and Mn co-doped In₂S₃/ZnS quantum dots with tunable emission for dual-modal targeted imaging

Pei Yu Lai, Chih Ching Huang, Tzung Han Chou, Keng-Liang Ou, Jia Yaw Chang

Research output: Contribution to journal › Article

8 Citations (Scopus)

Abstract

Here, we present the microwave-assisted synthesis of In₂S₃/ZnS core/shell quantum dots (QDs) co-doped with Ag⁺ and Mn²⁺ (referred to as AgMn:In₂S₃/ZnS). Ag⁺ altered the optical properties of the host QDs, whereas the spin magnetic moment (S =5/2) of Mn²⁺ efficiently induced the longitudinal relaxation of water protons. To the best of our knowledge, this is the first report of the aqueous synthesis of color-tunable AgMn:In₂S₃/ZnS core/shell QDs with magnetic properties. The synthetic procedure is rapid, facile, reproducible, and scalable. The obtained QDs offered a satisfactory quantum yield (45%), high longitudinal relaxivity (6.84s^-1 mM^-1), and robust photostability. In addition, they exhibited excellent stability over a wide pH range (5-12) and high ionic strength (0.15-2.0M NaCl). As seen by confocal microscopy and magnetic resonance imaging, AgMn:In₂S₃/ZnS conjugated to hyaluronic acid (referred to as AgMn:In₂S₃/ZnS@HA) efficiently and specifically targeted cluster determinant 44, a receptor overexpressed on cancer cells. Moreover, AgMn:In₂S₃/ZnS@HA showed negligible cytotoxicity in vitro and in vivo, rendering it a promising diagnostic probe for dual-modal imaging in clinical applications. Statement of Significance: In this manuscript, we reported a facial and rapid method to prepare In₂S₃/ZnS core/shell quantum dots (QDs) co-doped with Ag⁺ and Mn²⁺ (referred to as AgMn:In₂S₃/ZnS). Ag⁺ dopants were used to alter the optical properties of the In₂S₃ host, whereas Mn²⁺ co-dopants with their unpaired electrons provided paramagnetic properties. The emission wavelength of the core/shell QDs could be tuned from 550 to 743nm with a maximum PL quantum yield of 45%. The resulting core/shell QDs also maintained a stable emission in aqueous solution at broad ranges of pH (5-12) and ionic strength (0.15-2.0M NaCl), as well as a high photostability under continuous irradiation. In vivo cytotoxicity experiments showed that up to 500μg/mL AgMn:In₂S₃/ZnS@HA did not cause obvious toxicity to zebrafish embryos. In vitro targeted cell luminescence and magnetic resonance imaging showed that AgMn:In₂S₃/ZnS conjugated to hyaluronic acid was selectively and efficiently internalized in CD44-expressing tumor cells, confirming that the resultant QDs could function as dual-modal imaging probes for accurate diagnosis.

Original language	English
Journal	Acta Biomaterialia
DOIs	https://doi.org/10.1016/j.actbio.2016.12.028
Publication status	Accepted/In press - Sep 3 2016

Fingerprint

Quantum Dots

Semiconductor quantum dots

Imaging techniques

Hyaluronic acid

Quantum yield

Hyaluronic Acid

Magnetic resonance

Cytotoxicity

Ionic strength

Osmolar Concentration

Optical properties

Cells

Doping (additives)

Magnetic Resonance Imaging

Confocal microscopy

Zebrafish

Microwaves

Luminescence

Magnetic moments

Confocal Microscopy

Keywords

Hyaluronic acid
InS
Luminescence probe
Quantum dots
T1-weighted images

ASJC Scopus subject areas

Biotechnology
Biochemistry
Biomaterials
Biomedical Engineering
Molecular Biology

Cite this

Lai, P. Y., Huang, C. C., Chou, T. H., Ou, K-L., & Chang, J. Y. (Accepted/In press). Aqueous synthesis of Ag and Mn co-doped In₂S₃/ZnS quantum dots with tunable emission for dual-modal targeted imaging. Acta Biomaterialia. https://doi.org/10.1016/j.actbio.2016.12.028

Aqueous synthesis of Ag and Mn co-doped In₂S₃/ZnS quantum dots with tunable emission for dual-modal targeted imaging. / Lai, Pei Yu; Huang, Chih Ching; Chou, Tzung Han; Ou, Keng-Liang; Chang, Jia Yaw.

In: Acta Biomaterialia, 03.09.2016.

Research output: Contribution to journal › Article

Lai, PY, Huang, CC, Chou, TH, Ou, K-L & Chang, JY 2016, 'Aqueous synthesis of Ag and Mn co-doped In₂S₃/ZnS quantum dots with tunable emission for dual-modal targeted imaging', Acta Biomaterialia. https://doi.org/10.1016/j.actbio.2016.12.028

Lai PY, Huang CC, Chou TH, Ou K-L, Chang JY. Aqueous synthesis of Ag and Mn co-doped In₂S₃/ZnS quantum dots with tunable emission for dual-modal targeted imaging. Acta Biomaterialia. 2016 Sep 3. https://doi.org/10.1016/j.actbio.2016.12.028

Lai, Pei Yu ; Huang, Chih Ching ; Chou, Tzung Han ; Ou, Keng-Liang ; Chang, Jia Yaw. / Aqueous synthesis of Ag and Mn co-doped In₂S₃/ZnS quantum dots with tunable emission for dual-modal targeted imaging. In: Acta Biomaterialia. 2016.

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abstract = "Here, we present the microwave-assisted synthesis of In2S3/ZnS core/shell quantum dots (QDs) co-doped with Ag+ and Mn2+ (referred to as AgMn:In2S3/ZnS). Ag+ altered the optical properties of the host QDs, whereas the spin magnetic moment (S =5/2) of Mn2+ efficiently induced the longitudinal relaxation of water protons. To the best of our knowledge, this is the first report of the aqueous synthesis of color-tunable AgMn:In2S3/ZnS core/shell QDs with magnetic properties. The synthetic procedure is rapid, facile, reproducible, and scalable. The obtained QDs offered a satisfactory quantum yield (45{\%}), high longitudinal relaxivity (6.84s-1 mM-1), and robust photostability. In addition, they exhibited excellent stability over a wide pH range (5-12) and high ionic strength (0.15-2.0M NaCl). As seen by confocal microscopy and magnetic resonance imaging, AgMn:In2S3/ZnS conjugated to hyaluronic acid (referred to as AgMn:In2S3/ZnS@HA) efficiently and specifically targeted cluster determinant 44, a receptor overexpressed on cancer cells. Moreover, AgMn:In2S3/ZnS@HA showed negligible cytotoxicity in vitro and in vivo, rendering it a promising diagnostic probe for dual-modal imaging in clinical applications. Statement of Significance: In this manuscript, we reported a facial and rapid method to prepare In2S3/ZnS core/shell quantum dots (QDs) co-doped with Ag+ and Mn2+ (referred to as AgMn:In2S3/ZnS). Ag+ dopants were used to alter the optical properties of the In2S3 host, whereas Mn2+ co-dopants with their unpaired electrons provided paramagnetic properties. The emission wavelength of the core/shell QDs could be tuned from 550 to 743nm with a maximum PL quantum yield of 45{\%}. The resulting core/shell QDs also maintained a stable emission in aqueous solution at broad ranges of pH (5-12) and ionic strength (0.15-2.0M NaCl), as well as a high photostability under continuous irradiation. In vivo cytotoxicity experiments showed that up to 500μg/mL AgMn:In2S3/ZnS@HA did not cause obvious toxicity to zebrafish embryos. In vitro targeted cell luminescence and magnetic resonance imaging showed that AgMn:In2S3/ZnS conjugated to hyaluronic acid was selectively and efficiently internalized in CD44-expressing tumor cells, confirming that the resultant QDs could function as dual-modal imaging probes for accurate diagnosis.",

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AU - Huang, Chih Ching

AU - Chou, Tzung Han

AU - Ou, Keng-Liang

AU - Chang, Jia Yaw

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N2 - Here, we present the microwave-assisted synthesis of In2S3/ZnS core/shell quantum dots (QDs) co-doped with Ag+ and Mn2+ (referred to as AgMn:In2S3/ZnS). Ag+ altered the optical properties of the host QDs, whereas the spin magnetic moment (S =5/2) of Mn2+ efficiently induced the longitudinal relaxation of water protons. To the best of our knowledge, this is the first report of the aqueous synthesis of color-tunable AgMn:In2S3/ZnS core/shell QDs with magnetic properties. The synthetic procedure is rapid, facile, reproducible, and scalable. The obtained QDs offered a satisfactory quantum yield (45%), high longitudinal relaxivity (6.84s-1 mM-1), and robust photostability. In addition, they exhibited excellent stability over a wide pH range (5-12) and high ionic strength (0.15-2.0M NaCl). As seen by confocal microscopy and magnetic resonance imaging, AgMn:In2S3/ZnS conjugated to hyaluronic acid (referred to as AgMn:In2S3/ZnS@HA) efficiently and specifically targeted cluster determinant 44, a receptor overexpressed on cancer cells. Moreover, AgMn:In2S3/ZnS@HA showed negligible cytotoxicity in vitro and in vivo, rendering it a promising diagnostic probe for dual-modal imaging in clinical applications. Statement of Significance: In this manuscript, we reported a facial and rapid method to prepare In2S3/ZnS core/shell quantum dots (QDs) co-doped with Ag+ and Mn2+ (referred to as AgMn:In2S3/ZnS). Ag+ dopants were used to alter the optical properties of the In2S3 host, whereas Mn2+ co-dopants with their unpaired electrons provided paramagnetic properties. The emission wavelength of the core/shell QDs could be tuned from 550 to 743nm with a maximum PL quantum yield of 45%. The resulting core/shell QDs also maintained a stable emission in aqueous solution at broad ranges of pH (5-12) and ionic strength (0.15-2.0M NaCl), as well as a high photostability under continuous irradiation. In vivo cytotoxicity experiments showed that up to 500μg/mL AgMn:In2S3/ZnS@HA did not cause obvious toxicity to zebrafish embryos. In vitro targeted cell luminescence and magnetic resonance imaging showed that AgMn:In2S3/ZnS conjugated to hyaluronic acid was selectively and efficiently internalized in CD44-expressing tumor cells, confirming that the resultant QDs could function as dual-modal imaging probes for accurate diagnosis.

AB - Here, we present the microwave-assisted synthesis of In2S3/ZnS core/shell quantum dots (QDs) co-doped with Ag+ and Mn2+ (referred to as AgMn:In2S3/ZnS). Ag+ altered the optical properties of the host QDs, whereas the spin magnetic moment (S =5/2) of Mn2+ efficiently induced the longitudinal relaxation of water protons. To the best of our knowledge, this is the first report of the aqueous synthesis of color-tunable AgMn:In2S3/ZnS core/shell QDs with magnetic properties. The synthetic procedure is rapid, facile, reproducible, and scalable. The obtained QDs offered a satisfactory quantum yield (45%), high longitudinal relaxivity (6.84s-1 mM-1), and robust photostability. In addition, they exhibited excellent stability over a wide pH range (5-12) and high ionic strength (0.15-2.0M NaCl). As seen by confocal microscopy and magnetic resonance imaging, AgMn:In2S3/ZnS conjugated to hyaluronic acid (referred to as AgMn:In2S3/ZnS@HA) efficiently and specifically targeted cluster determinant 44, a receptor overexpressed on cancer cells. Moreover, AgMn:In2S3/ZnS@HA showed negligible cytotoxicity in vitro and in vivo, rendering it a promising diagnostic probe for dual-modal imaging in clinical applications. Statement of Significance: In this manuscript, we reported a facial and rapid method to prepare In2S3/ZnS core/shell quantum dots (QDs) co-doped with Ag+ and Mn2+ (referred to as AgMn:In2S3/ZnS). Ag+ dopants were used to alter the optical properties of the In2S3 host, whereas Mn2+ co-dopants with their unpaired electrons provided paramagnetic properties. The emission wavelength of the core/shell QDs could be tuned from 550 to 743nm with a maximum PL quantum yield of 45%. The resulting core/shell QDs also maintained a stable emission in aqueous solution at broad ranges of pH (5-12) and ionic strength (0.15-2.0M NaCl), as well as a high photostability under continuous irradiation. In vivo cytotoxicity experiments showed that up to 500μg/mL AgMn:In2S3/ZnS@HA did not cause obvious toxicity to zebrafish embryos. In vitro targeted cell luminescence and magnetic resonance imaging showed that AgMn:In2S3/ZnS conjugated to hyaluronic acid was selectively and efficiently internalized in CD44-expressing tumor cells, confirming that the resultant QDs could function as dual-modal imaging probes for accurate diagnosis.

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KW - InS

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KW - T1-weighted images

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10.1016/j.actbio.2016.12.028