Ag掺杂HgS量子点: 一种pH调谐的近红外Ⅱ区荧光纳米探针

doi:10.15541/jim20190031

无机材料学报 ›› 2019, Vol. 34 ›› Issue (11): 1156-1160.DOI: 10.15541/jim20190031 CSTR: 32189.14.10.15541/jim20190031

Ag掺杂HgS量子点: 一种pH调谐的近红外Ⅱ区荧光纳米探针

王君诚¹,杨菲菲²,高冠斌¹(),孙涛垒^1,²()

^1. 武汉理工大学材料复合新技术国家重点实验室
^2. 武汉理工大学化学化工与生命科学学院, 武汉 430070

收稿日期:2019-01-16 修回日期:2019-04-18 出版日期:2019-11-20 网络出版日期:2019-05-29
作者简介:王君诚(1993-), 男, 硕士研究生. E-mail: wangjuncheng@whut.edu.cn
基金资助:
国家自然科学基金(21805218);国家自然科学基金(51873168);国家自然科学基金(51533007);国家自然科学基金(21975191);湖北省自然科学基金(2018CFA002);湖北省自然科学基金(2018CFB348)

Ag doped HgS Quantum Dots: a pH-tunable Near-infrared-Ⅱ Fluorescent Nanoprobe

WANG Jun-Cheng¹,YANG Fei-Fei²,GAO Guan-Bin¹(),SUN Tao-Lei^1,²()

^1. State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China
^2. School of Chemistry, Chemical Engineering and Life Science, Wuhan University of Technology, Wuhan 430070, China

Received:2019-01-16 Revised:2019-04-18 Published:2019-11-20 Online:2019-05-29
Supported by:
National Natural Science Foundation of China(21805218);National Natural Science Foundation of China(51873168);National Natural Science Foundation of China(51533007);National Natural Science Foundation of China(21975191);Natural Science Foundation of Hubei Province(2018CFA002);Natural Science Foundation of Hubei Province(2018CFB348)

摘要/Abstract

摘要：

近红外荧光特别是近红外Ⅱ区(1000~1700 nm)荧光在生物体内具有高组织渗透率、高时空分辨率、低背景荧光干扰和低光损伤的特点, 因此发展水溶性与生物相容性良好、量子产率高的长波段近红外荧光探针意义重大。本研究制备了不同荧光发射的Ag掺杂HgS量子点(HgAgS量子点)。在不同pH溶液中制备的HgAgS量子点荧光发射峰位于近红外Ⅱ区, 且呈现规律性变化; 随pH的增大, HgAgS量子点荧光发射峰先红移而后蓝移, 发射波长在pH 6时达到最大1110 nm; 原子吸收光谱表明在不同pH溶液中制备的HgAgS量子点, Ag的掺杂量(Ag/Hg比值)呈现出与荧光发射峰相同的规律性变化, 证明通过pH调控Ag的掺杂量从而调谐荧光发射峰的位置。HgAgS量子点的量子产率随pH先增加后降低, 在pH 7时达到最大13.23%(λ_em=1100 nm)。细胞毒性实验表明Ag的掺杂量对HgAgS量子点的细胞毒性无明显影响, 在1~50 μg/L浓度范围内均无明显细胞毒性。本研究结果不仅为体内进行近红外荧光成像提供了基础研究数据, 而且为荧光纳米探针的设计与制备提出了新的见解。

关键词: 近红外Ⅱ区荧光, HgAgS量子点, pH调谐, 热注射法

Abstract:

Design and preparation of near-infrared (NIR) especially NIR-Ⅱ (1000-1700 nm) fluorescence probe with favorable biocompatibility and high quantum yield have become the focus of noninvasive fluorescent imaging in recent years. In this study, Ag doped HgS QDs (HgAgS QDs) were prepared at different synthetic pH. With the increase of pH, the fluorescence emission peak of the HgAgS QDs red-shifted and then blue-shifted, reaching a maximum emission wavelength of 1110 nm (QY=8.12%) at pH 6.0. Atomic absorption spectroscopy showed that the doping amount of Ag (Ag/Hg ratio) changed regularly in HgAgS QDs prepared at different pH solutions, which was consistent with change of fluorescence emission position. It was proved that pH could tune the position of fluorescence emission peak by adjusting the doping amount of Ag. Moreover, the quantum yield (QY) of HgAgS QDs increased firstly and then decreased, presenting an optimum of 13.23% (λ_em=1100 nm) at pH 7.0. Cell viability tests demonstrated that the doping amount of Ag showed no significant effect on cytotoxicity. And all HgAgS QDs had no cytotoxicity at the concentration range of 1-50 μg/L, thus can be used as a pH-tunable NIR-Ⅱ fluorescent probe. These findings provide a promising application in the NIR fluorescent imaging and an interesting insight into the design and preparation of the NIR-Ⅱ fluorescence nanoprobe.

Key words: NIR-Ⅱ fluorescence, HgAgS quantum dots, pH-tunable, hot injection

中图分类号:

TQ174

王君诚, 杨菲菲, 高冠斌, 孙涛垒. Ag掺杂HgS量子点: 一种pH调谐的近红外Ⅱ区荧光纳米探针[J]. 无机材料学报, 2019, 34(11): 1156-1160.

WANG Jun-Cheng, YANG Fei-Fei, GAO Guan-Bin, SUN Tao-Lei. Ag doped HgS Quantum Dots: a pH-tunable Near-infrared-Ⅱ Fluorescent Nanoprobe[J]. Journal of Inorganic Materials, 2019, 34(11): 1156-1160.

图/表 9

图1 HgAgS量子点的X射线衍射图谱(a), 透射电子显微镜照片(b), 高分辨透射电镜照片(c)和粒径统计分布图(d)

Fig. 1 XRD pattern (a), TEM image (b), HR-TEM image (c), and size distribution (d) of HgAgS QDs

图2 HgAgS量子点的扫描透射电子显微镜高角环形暗场照片(HAADF) (a)和能谱图(b), 及其Ag(蓝色)、Hg(红色)和S(黄色)三种元素混合(c)和对应的单一元素Ag(d)、Hg(e)和S(f)分布图

Fig. 2 High-angle annular dark field (HAADF), STEM image (a) and EDS (b) of HgAgS QDs; Mixed elements mapping of HgAgS QDs (c) with corresponding single element Ag(blue) (d), Hg(red) (e) and S(yellow) (f) elements distribution

图3 卡托普利和HgAgS量子点的傅里叶红外变换光谱

Fig. 3 FT-IR spectra of captopril and HgAgS QDs

图4 激发波长为400 nm时在不同pH下制备的HgAgS量子点的荧光光谱(a)及其Ag/Hg值变化(彩图见网页)

Fig. 4 Fluorescence (a) and Ag/Hg value (b) of HgAgS QDs with different synthetic pH (Ex=400 nm) (colourful edition is available on website)

图5 HgAgS量子点(pH=6.0制备)在不同时间下对INS-1细胞的细胞活性影响(a)和不同pH条件下制备的HgAgS量子点对PC12细胞的活性影响(b)

Fig. 5 Cell viability of HgAgS QDs prepared at pH 6.0 on INS-1 cells for 24 and 48 h (a), and cell viability of HgAgS QDs prepared at pH=3.0, 5.0, 6.0 and 11.0 on PC12 cells (b). Concentrations of HgAgS QDs were 0, 1, 10, 20 and 50 μg/L

图6 图S1 在pH=5(a), 9(b)和11(c)溶液中制备的HgAgS量子点的HR-TEM 照片

Fig. 6 Fig. S1 HR-TEM images of HgAgS QDs synthesized at pH 5 (a), 9 (b) and 11 (c)

图7 图S2 HgAgS量子点的水合粒径

Fig. 7 Fig. S2 Hydrate particle size of HgAgS QDs

图8 图S3 HgS量子点(黑色曲线)和HgAgS量子点(红色曲线)的全谱(a)、Ag3d(b)、Hg4f(c)和S2p(d)的特征谱

Fig. 8 Fig. S3 Survey spectra (a), Ag3d (b), Hg4f (c) and S2p (d) spectra of HgS QDs (black curves) and HgAgS QDs (red curves)

图9 图S4 HgAgS量子点的荧光量子产率, 激发波长为400 nm

Fig. 9 Fig. S4 QYs of HgAgS QDs, Ex = 400 nm

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Ag掺杂HgS量子点: 一种pH调谐的近红外Ⅱ区荧光纳米探针

Ag doped HgS Quantum Dots: a pH-tunable Near-infrared-Ⅱ Fluorescent Nanoprobe

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