Ag2S基近红外II区荧光量子点的水相合成优化探究

doi:10.6023/A21070333

化学学报 ›› 2021, Vol. 79 ›› Issue (10): 1281-1285.DOI: 10.6023/A21070333 上一篇下一篇

研究论文

Ag₂S基近红外II区荧光量子点的水相合成优化探究

余梦^b, 张子俊^a, 朱国委^a, 谷振华^a, 段玉霖^a, 余良翀^a, 高冠斌^a^,^*(), 孙涛垒^a^,^b^,^*()

a 武汉理工大学材料复合新技术国家重点实验室武汉 430070
b 武汉理工大学化学化工与生命科学学院武汉 430070

投稿日期:2021-07-16 发布日期:2021-08-13
通讯作者: 高冠斌, 孙涛垒
作者简介:
† 共同第一作者
基金资助:
国家自然科学基金(21975191); 国家自然科学基金(21805218); 国家自然科学基金(51873168); 国家级大学生创新创业训练计划(202110497008)

Synthesis of Ag₂S Based Quantum Dots with Near-infrared-II Fluorescence Emission in Water

Meng Yu^b, Zijun Zhang^a, Guowei Zhu^a, Zhenhua Gu^a, Yulin Duan^a, Liangchong Yu^a, Guanbin Gao^a(), Taolei Sun^a^,^b()

a State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070
b School of Chemistry, Chemical Engineering and Life Science, Wuhan University of Technology, Wuhan 430070

Received:2021-07-16 Published:2021-08-13
Contact: Guanbin Gao, Taolei Sun
About author:
† These authors contributed equally to this work
Supported by:
National Natural Science Foundation of China(21975191); National Natural Science Foundation of China(21805218); National Natural Science Foundation of China(51873168); National innovation and Entrepreneurship Training Program for College Students(202110497008)

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摘要/Abstract

具有近红外II区荧光的Ag₂S量子点(QDs)因具有带隙窄、Stokes位移大及光稳定性好等优点而在生物成像领域具有广阔应用前景. 然而, 传统有机相合成的Ag₂S量子点水溶性与生物相容性较差, 而水相合成Ag₂S量子点的荧光又很难到近红外II区, 这严重制约了Ag₂S量子点的生物医学应用推广. 因此, 优化探究具有近红外II区荧光发射的Ag₂S基量子点的水相合成方法具有重要意义. 采用核掺杂ZnS、表面阳离子(Zn²⁺)改性以及调控表面配体制备出一系列Ag₂S基量子点, 发现核掺杂和表面阳离子改性均使Ag₂S基量子点的荧光呈现剂量依赖性蓝移; 而将表面配体由树枝状短链(Captopril)更换为长直链(11-巯基十一烷酸, MUA)时, Ag₂S基量子点的发射峰红移至1105 nm(近红外II区)且半峰宽更窄. 本研究发现, 相比核掺杂和表面阳离子改性, 优化表面配体更容易在水相中制备出具有近红外II区荧光的Ag₂S基量子点. 本工作为近红外荧光量子点的水相合成及优化提供了基础研究数据.

关键词: 近红外II区荧光, Ag₂S基量子点, 水相合成, 核掺杂, 表面阳离子改性, 优化表面配体

Growing numbers of quantum dots (QDs) have been applied in biological fluorescence imaging, especially those QDs with near-infrared-II fluorescence emission, avoiding the interference of autofluorescence of biological tissues, have broad application prospects in the field of fluorescence imaging. In particularly, Ag₂S quantum dots (Ag₂S QDs) have drew great attention of researchers in biological fluorescence imaging due to the near-infrared fluorescence emission, large Stokes shift, good light and chemical stability. However, the Ag₂S QDs synthesized in organic phase usually experienced poor water solubility and biocompatibility, while the fluorescence of the Ag₂S QDs synthesized in aqueous phase is difficult to reach the near-infrared-II region, which severely restricts the promotion of Ag₂S QDs in biological fluorescence imaging. Therefore, it is of great significance to optimize and explore the water-phase synthesis method of Ag₂S based quantum dots with near-infrared-II fluorescence emission. The goal of this work is to synthesize Ag₂S QDs with near-infrared-II region fluorescence emission by aqueous phase method. First, captopril modified Ag₂S QDs (Ag₂S@Cap QDs) were prepared in water, and its fluorescence emission peak lied in the near-infrared-II region at 1005 nm. Then a series of Zn:Ag₂S@Cap QDs were prepared in aqueous by introducing ZnS to the Ag₂S core. The results showed that the fluorescence emission peaks of Zn:Ag₂S@Cap QDs blue shifted in a core-doping ZnS-dose dependent manner. Next, a series of Ag₂S@Cap-Zn QDs were prepared in aqueous by introducing Zn²⁺ to the ligand-shell of Ag₂S QDs. The fluorescence emission peaks of these Ag₂S@Cap-Zn QDs also blue shifted in a Zn²⁺-dose dependent manner. Finally, Ag₂S@MUA QDs were prepared by replacing the shell ligand from Cap to 11-mercaptoundecanoic acid (MUA). The fluorescence emission peak of these Ag₂S@MUA QDs red shifted to 1105 nm, locating in the near-infrared-II region, and the width of the fluorescence curve at half-maximum height became narrower, implying better application prospect in biological fluorescence imaging. This work not only successfully prepared a kind of Ag₂S QDs with near-infrared-II fluorescence emission in aqueous phase, but also opened an avenue for the preparation and optimization of semiconductor QDs with near-infrared fluorescence.

Key words: near-infrared-Ⅱ fluorescence, Ag₂S QDs, aqueous synthesis, core-doping, cationic-modification, optimizing surface ligand

引用此文

余梦, 张子俊, 朱国委, 谷振华, 段玉霖, 余良翀, 高冠斌, 孙涛垒. Ag₂S基近红外II区荧光量子点的水相合成优化探究[J]. 化学学报, 2021, 79(10): 1281-1285.

Meng Yu, Zijun Zhang, Guowei Zhu, Zhenhua Gu, Yulin Duan, Liangchong Yu, Guanbin Gao, Taolei Sun. Synthesis of Ag₂S Based Quantum Dots with Near-infrared-II Fluorescence Emission in Water[J]. Acta Chimica Sinica, 2021, 79(10): 1281-1285.

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图/表 4

图1. Ag2S@Cap量子点的(a) TEM图(插图: 高分辨细节图)、(b)水合粒径、(c) Zeta电势、(d) Ag2S@CapS量子点(黑色)和Cap(红色)的傅里叶红外光谱图、(e) Ag2S@Cap量子点的紫外-可见光光谱图和(f) Ag2S@Cap量子点近红外荧光光谱图

Figure 1. (a) TEM image of Ag2S@Cap QDs (insert: high resolution image), (b) hydrated particle size of Ag2S@Cap QDs, (c) Zeta potential of Ag2S@Cap QDs, (d) FT-IR spectra of Ag2S@Cap QDs (black curve) and Cap (red curve), (e) UV-Vis absorption spectrum of Ag2S@Cap QDs, and (f) near-infrared fluorescence spectrum of Ag2S@Cap QDs

图2. (a)核掺杂Zn:Ag2S@Cap量子点的扫描透射电子显微镜高角环形暗场照片(HAADF), 电子能谱扫描得到的Ag (b)、S (c)和 Zn (d)原子分布图及三种核掺杂Zn:Ag2S@Cap与Ag2S@Cap量子点的水合粒径(e)、Zeta电势(f)、傅里叶红外光谱(g)和近红外荧光光谱(h)图.

Figure 2. (a) HAADF images of Zn:Ag2S@Cap QDs via core doping ZnS, single element of Ag (b), S (c) and Zn (d) distribution by EDS mapping, hydrated particle size (e), Zeta potential (f), FT-IR spectra (g) and near-infrared fluorescence spectra (h) of Ag2S@Cap QDs and three Zn:Ag2S@Cap QDs core-doped with different dose of ZnS

图3. (a)阳离子改性制备Ag2S@Cap-Zn量子点的扫描透射电子显微镜高角环形暗场照片(HAADF), 电子能谱扫描得到的Ag (b)、S (c)和Zn (d)原子分布图以及三种表面Zn2+阳离子改性Ag2S@Cap-Zn与Ag2S@Cap量子点的水合粒径(e)、Zeta电势(f)、傅里叶红外光谱(g)和近红外荧光光谱(h)图

Figure 3. (a) HAADF images of Ag2S@Cap-Zn QDs prepared by ligand cationic modification of Zn2+, single element of Ag (b), S (c) and Zn (d) distribution by EDS mapping, hydrated particle size (e), Zeta potential (f), FT-IR spectra (g) and near-infrared fluorescence spectra (h) of Ag2S@Cap QDs and three Ag2S@Cap-Zn QDs prepared by ligand cationic modification of Zn2+ with different doses

图4. (a) Ag2S@MUA量子点的TEM图(插图为高分辨细节图)、Ag2S@Cap与Ag2S@MUA量子点的(b)水合粒径图及(c) Zeta电势、(d) Ag2S@MUA量子点和MUA的傅里叶红外光谱和Ag2S@Cap与Ag2S@MUA量子点的(e)紫外-可见吸收光谱图及(f)近红外荧光光谱图

Figure 4. (a) TEM image of Ag2S@MUA QDs (insert: high resolution image), (b) hydrated particle size and (c) Zeta potential of Ag2S@Cap QDs and Ag2S@MUA QDs, (d) FT-IR spectra of Ag2S@MUA QDs and MUA and (e) UV-Vis absorption spectra and (f) near-infrared fluorescence spectra of Ag2S@Cap QDs and Ag2S@MUA QDs

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Ag₂S基近红外II区荧光量子点的水相合成优化探究

Synthesis of Ag₂S Based Quantum Dots with Near-infrared-II Fluorescence Emission in Water

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