Template-Based Controlled Synthesis and Bioapplication of AgInSe2:Zn2+ Near-Infrared Luminescent Quantum Dots※

doi:10.6023/A21120606

Acta Chimica Sinica ›› 2022, Vol. 80 ›› Issue (5): 625-632.DOI: 10.6023/A21120606 Previous Articles Next Articles

Special Issue: 中国科学院青年创新促进会合辑

Article

模板法控制合成AgInSe₂:Zn²⁺近红外荧光量子点及其生物标记应用^※

廉纬^a^,^b, 方泽铠^a^,^b, 涂大涛^a^,^b^,^c^,^*(), 李嘉尧^a^,^b, 韩思远^b, 李仁富^b^,^c, 商晓颖^b^,^c, 陈学元^a^,^b^,^c^,^*()

a 福州大学化学学院福州 350108
b 中国科学院福建物质结构研究所中国科学院功能纳米结构设计与组装重点实验室福州 350002
c 中国科学院福建物质结构研究所结构化学国家重点实验室福州 350002

投稿日期:2021-12-30 发布日期:2022-05-31
通讯作者: 涂大涛, 陈学元
作者简介:
^※庆祝中国科学院青年创新促进会十年华诞.
基金资助:
国家自然科学基金(U1805252); 国家自然科学基金(21975257); 国家自然科学基金(22135008); 福建省自然科学基金(2019I0029); 福建省自然科学基金(2021L3024)

Template-Based Controlled Synthesis and Bioapplication of AgInSe₂:Zn²⁺ Near-Infrared Luminescent Quantum Dots^※

Wei Lian^a^,^b, Zekai Fang^a^,^b, Datao Tu^a^,^b^,^c(), Jiayao Li^a^,^b, Siyuan Han^b, Renfu Li^b^,^c, Xiaoying Shang^b^,^c, Xueyuan Chen^a^,^b^,^c()

a College of Chemistry, Fuzhou University, Fuzhou 350108, China
b CAS Key Laboratory of Design and Assembly of Functional Nanostructures, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China
c State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China

Received:2021-12-30 Published:2022-05-31
Contact: Datao Tu, Xueyuan Chen
About author:
^※Dedicated to the 10th anniversary of the Youth Innovation Promotion Association, CAS.
Supported by:
National Natural Science Foundation of China(U1805252); National Natural Science Foundation of China(21975257); National Natural Science Foundation of China(22135008); Natural Science Foundation of Fujian Province(2019I0029); Natural Science Foundation of Fujian Province(2021L3024)

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Abstract

AgInSe₂ (AISe) quantum dots (QDs) exhibit large Stokes shift, composition-dependent photoluminescence (PL), long PL lifetimes and low toxicity, making them exceptional candidates in a wide variety of bioapplications. However, it remains notoriously challenging to precisely control both the morphology and composition to optimize the PL performance of AISe QDs via conventional direct synthesis. Herein, we develop the unique low-temperature (75 ℃) template-based synthesis of highly efficient near-infrared (NIR) luminescent AISe QDs from In₂Se₃ QDs via a facile cation exchange method. The brief synthesis AISe QDs process was as follows: firstly, indium acetate was dissolved in non-coordinating solvent octadecene. Selenium precursor was injected into the above mixture at 200 ℃, followed by nucleation and growth within a few minutes. Thereafter, In₂Se₃ template QDs can be acquired, and the dispersity of the as-prepared QDs can be improved by adding zinc. Secondly, silver acetate was added to the In₂Se₃:Zn²⁺ QDs solution with stirring for 15 min at 75 ℃. Finally, AgInSe₂:Zn²⁺ QDs were obtained. The proposed method enables the as-prepared AISe QDs to inherit the size and morphology of the template QDs. The extent of cation exchange can be controlled by rationally manipulating the Ag/In precursor molar ratio. We successfully regulate the stoichiometry of Ag/In ratio from 0.26 to 1.09. As a result, highly efficient luminescence of AISe QDs with the maximum absolute quantum yield of 42.5% has been achieved, which is higher than that of the AISe counterparts synthesized via the direct method. Moreover, we survey the luminescence mechanism of AISe QDs by means of the steady-state, transient and temperature-dependent spectroscopies. AISe nanoprobes were prepared by coating the hydrophobic QDs with a layer of 1,2-distearoyl-sn-glycero-3-phosphoethanol-amine-N-[biotin(polyethyleneglycol)- 2000] (DSPE-PEG-Biotin) phospholipids through hydrophobic interaction. By virtue of the excellent biocompatibility and intense NIR emission, we exemplify the application of AISe nanoprobes in the targeted cancer cell imaging, thus revealing their promising bioapplications including disease diagnosis and imaging-guided surgery.

Key words: AgInSe₂, near-infrared, quantum dots, cation exchange, luminescent nanoprobes

Cite this article

Wei Lian, Zekai Fang, Datao Tu, Jiayao Li, Siyuan Han, Renfu Li, Xiaoying Shang, Xueyuan Chen. Template-Based Controlled Synthesis and Bioapplication of AgInSe₂:Zn²⁺ Near-Infrared Luminescent Quantum Dots^※[J]. Acta Chimica Sinica, 2022, 80(5): 625-632.

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Fig. & Tab. 6

Figure 1. (a) Transmission electron microscopy (TEM) images of In2Se3:Zn2+ QDs with precursor ratios of Zn/In of (a1) 0, (a2) 0.2, (a3) 0.4, (a4) 0.6 and (a5) 0.8, respectively; (b) TEM images of AgInSe2:Zn2+ QDs with precursor ratios of Ag/In of (b1) 0, (b2) 0.3, (b3) 0.6, (b4) 0.9 and (b5) 1.2, respectively. Insets show their corresponding size distribution histogram by randomly calculating 100 particles in the TEM images

Figure 2. XPS analyses of (a) In2Se3:Zn2+ and (b) AgInSe2:Zn2+ QDs. XPS scans on (c) Ag 3d and (d) In 3d of AgInSe2:Zn2+ QDs with different precursor molar ratio of Ag/In

Figure 3. (a) Absorption spectra, (b) PL emission spectra (λex=365 nm), and (c) PL decays upon excitation at 375 nm by monitoring the peak emission of In2Se3:Zn2+ QDs with different precursor molar ratio of Zn/In. (d) Absorption spectra, (e) PL emission spectra (λex=365 nm), and (f) PL decays upon excitation at 375 nm by monitoring the peak emission of AgInSe2:Zn2+ QDs with different precursor molar ratio of Ag/In. Insets show their corresponding photographs of QDs dispersed in cyclohexane solution

Figure 4. (a) Temperature-dependent emission spectra of the In2Se3:Zn2+ QDs upon excitation at 365 nm, (b) PL intensities as a function of temperature in (a). (c) Temperature-dependent emission spectra of the AgInSe2:Zn2+ QDs upon excitation at 365 nm, (d) PL intensities as a function of temperature in (c). (e) Schematic illustration showing the proposed PL process in AgInSe2:Zn2+ with different stoichiometry of Ag/In

Figure 5. (a) Schematic illustration of biotinylation of AgInSe2:Zn2+ QDs and photographs of OA-QDs and Biotin-QDs dispersed in hexane and water mixed solvent, respectively. (b) Fourier-transform infrared spectra of the OA-QDs and Biotin-QDs, (c) Zeta-potential and (d) hydrodynamic diameter distribution of Biotin-QDs dispersed in aqueous solution (pH 7.1)

Figure 6. (a) Schematic illustration of targeted cell imaging based on Biotin-QDs nanoprobe. Confocal laser scanning microscopy images of Biotin-QDs incubated with (b) HeLa cells and (c) L-02 cells after 2 h. Panel 1 is the bright-field images. DAPI stained cell nucleus images (λex=408 nm) that indicate the nuclear regions are shown in panel 2. Panel 3 is the PL images (λex=408 nm) of QDs, and panel 4 is the overlay images of panels 1, 2 and 3

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模板法控制合成AgInSe₂:Zn²⁺近红外荧光量子点及其生物标记应用^※

Template-Based Controlled Synthesis and Bioapplication of AgInSe₂:Zn²⁺ Near-Infrared Luminescent Quantum Dots^※

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模板法控制合成AgInSe2:Zn2+近红外荧光量子点及其生物标记应用※