金核/银壳纳米棒用于癌细胞的表面增强拉曼散射成像及肿瘤活体光谱检测

引用本文: 冯艳林, 王建霖, 宁鑫, 曹济民. 金核/银壳纳米棒用于癌细胞的表面增强拉曼散射成像及肿瘤活体光谱检测[J]. 分析化学, 2022, 50(8): 1196-1204. doi: 10.19756/j.issn.0253-3820.221016 shu

Citation: FENG Yan-Lin, WANG Jian-Lin, NING Xin, CAO Ji-Min. Au@Ag Core-Shell Nanorods for Surface Enhanced Raman Scattering Imaging of Cancer Cells and in Vivo Cancer Spectroscopic Detection[J]. Chinese Journal of Analytical Chemistry, 2022, 50(8): 1196-1204. doi: 10.19756/j.issn.0253-3820.221016 shu

金核/银壳纳米棒用于癌细胞的表面增强拉曼散射成像及肿瘤活体光谱检测

山西医科大学生理学系, 细胞生理学教育部重点实验室, 太原 030001

通讯作者: 曹济民,E-mail:caojimin@sxmu.edu.cn

基金项目:
国家自然科学基金项目(No.22007063)和山西省卫健委医学重点科技计划项目(No.2020XM01)资助。

摘要: 表面增强拉曼散射(SERS)是一种分子特有的超灵敏光谱技术。然而,现有的SERS主要限制在体外传感。银(Ag)材料因其优异的表面等离子体共振(SPR)特性成为使用最多的SERS基底。但是,Ag材料的低化学稳定性和生物相容性限制了其在生物医学中的应用。因此,提高Ag材料的SPR活性及稳定性成为拓宽其体内应用的研究重点。本研究通过化学沉积的方法,合成了一种金核/银壳纳米棒结构(Au@Ag NRs)。透射电镜(TEM)、扫描透射电子显微镜(STEM)、能量散色X射线元素扫描图(EDX)和X射线衍射(XRD)的检测结果表明成功合成了Au@Ag NRs。进一步偶联近红外拉曼分子二乙基硫吖啶羰基碘(DTTC)和巯基聚乙二醇(mPEG-SH)制备了p_DAu@Ag NRs。紫外-可见吸收光谱(UV-Vis)结果表明,p_DAu@Ag NRs在近红外区有很好的SPR特性,因此,p_DAu@Ag NRs具有很好的SERS性质。电感耦合等离子体发射光谱(ICP-OES)证明p_DAu@Ag NRs中Ag⁺的解离很少,说明p_DAu@Ag NRs的生物相容性良好。MTS (3-(4,5-二甲基噻唑-2-基)-5-(3-羧基甲氧基苯基)-2-(4-磺基苯基)-2H-四唑)测试结果进一步说明,p_DAu@Ag NRs具有良好的生物相容性,可用于细胞及生物体内传感。检测了p_DAu@Ag NRs在人乳腺癌细胞(MCF-7)的SERS成像及肿瘤活体传感的效果。结果表明,Au@Ag NRs对MCF-7细胞具有良好的SERS成像能力,并在肿瘤部位保持较高的SERS强度。本研究为乳腺癌早期成像及光谱学诊断提供了技术支持。

关键词:

English

Au@Ag Core-Shell Nanorods for Surface Enhanced Raman Scattering Imaging of Cancer Cells and in Vivo Cancer Spectroscopic Detection

Key Laboratory of Cellular Physiology, Ministry of Education, Department of Physiology, Shanxi Medical University, Taiyuan 030001, China

Corresponding author: CAO Ji-Min, caojimin@sxmu.edu.cn

Received Date: 11 January 2022
Revised Date: 13 April 2022
Fund Project:
Supported by the National Natural Science Foundation of China (No.22007063) and the Shanxi Medical Key Science and Technology Project Plan, China (No.2020XM01).

Abstract: Surface enhanced Raman scattering (SERS) is a molecular specific hypersensitive spectroscopy technique. However, the existing SERS are mainly limited to extracorporeal sensing. Silver (Ag) material has become the mostly used SERS substrate because of its excellent surface plasmon resonance (SPR) characteristics. However, poor chemical stability and biocompatibility limit its biomedical applications. Therefore, optimizing the SPR activity and stability of Ag materials has become the research focus to broaden its application in vivo. In this study, Au@Ag core-shell nanorods (Au@Ag NRs) were synthesized by chemical deposition. The detection results of transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), energy dispersive X-ray element mapping (EDX) and X-ray diffraction (XRD) proved that Au@Ag NRs were successfully synthesized. Then, the near infrared Raman molecules of diethylthioacridine carbonyl iodine (DTTC) and mercaptopolyethylene glycol (PEG-SH) were coupled to Au@Ag NRs (p_DAu@Ag NRs) to evaluate SERS properties both in vitro and in vivo. Ultraviolet visible spectrophotometer (UV-Vis) characterization revealed that p_DAu@Ag NRs had good SPR characteristics in the near infrared region, resulting in good SERS properties in vitro. Inductively coupled plasma optical emission spectroscopy (ICP-OES) showed little dissociation of Ag ions, which was not enough to cause biological toxicity. MTS (3-(4,5-dimethylthiazole-2-yl)-5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H tetrazole) test further confirmed that p_DAu@Ag NRs had good biocompatibility, ensuring the safe application in vivo. Finally, p_DAu@Ag NRs was used for Raman imaging of human breast cancer (MCF-7) cells and Raman biosensing in MCF-7 tumor-bearing mice. The results showed that Au@Ag NRs had excellent SERS imaging ability in MCF-7 cells and maintained high SERS activity on the tumor site. This technique may be helpful for early monitoring and spectroscopic diagnosis of breast cancer.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

金核/银壳纳米棒用于癌细胞的表面增强拉曼散射成像及肿瘤活体光谱检测

通讯作者: 曹济民,E-mail:caojimin@sxmu.edu.cn

English

Au@Ag Core-Shell Nanorods for Surface Enhanced Raman Scattering Imaging of Cancer Cells and in Vivo Cancer Spectroscopic Detection

Corresponding author: CAO Ji-Min, caojimin@sxmu.edu.cn

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

金核/银壳纳米棒用于癌细胞的表面增强拉曼散射成像及肿瘤活体光谱检测

通讯作者: 曹济民,E-mail:caojimin@sxmu.edu.cn

English

Au@Ag Core-Shell Nanorods for Surface Enhanced Raman Scattering Imaging of Cancer Cells and in Vivo Cancer Spectroscopic Detection

Corresponding author: CAO Ji-Min, caojimin@sxmu.edu.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs