负载银簇的硅基杂化纳米颗粒制备及其SERS性能

doi:10.15541/jim20210201

无机材料学报 ›› 2021, Vol. 36 ›› Issue (12): 1297-1304.DOI: 10.15541/jim20210201

所属专题：【虚拟专辑】生物检测与成像(2020~2021)

负载银簇的硅基杂化纳米颗粒制备及其SERS性能

文子聪¹(), 牛德超¹(), 李永生¹^,²()

1.华东理工大学材料科学与工程学院, 上海 200237
2.石河子大学化学化工学院, 石河子 832003

收稿日期:2021-03-23 修回日期:2021-05-18 出版日期:2021-12-20 网络出版日期:2021-07-12
通讯作者: 牛德超, 副教授. E-mail: dcniu@ecust.edu.cn;李永生, 教授. E-mail: ysli@ecust.edu.cn
作者简介:文子聪(1996-), 男, 硕士研究生. E-mail: mos15915333133@163.com
基金资助:
国家重点研发计划(2016YFA0203700);国家自然科学基金(52072124);上海市自然科学基金(20ZR1414900)

Silver Clusters-loaded Silica-based Hybrid Nanoparticles: Synthesis and SERS Performance

WEN Zicong¹(), NIU Dechao¹(), LI Yongsheng¹^,²()

1. School of Materials of Science and Engineering, East China University of Science and Technology, Shanghai 200237, China
2. School of Chemistry and Chemical Engineering, Shihezi University, Shihezi 832003, China

Received:2021-03-23 Revised:2021-05-18 Published:2021-12-20 Online:2021-07-12
Contact: NIU Dechao, associate professor. E-mail: dcniu@ecust.edu.cn;LI Yongsheng, professor. E-mail: ysli@ecust.edu.cn
About author:WEN Zicong(1996-), male, Master candidate. E-mail: mos15915333133@163.com
Supported by:
National Key Research and Development Program of China(2016YFA0203700);National Natural Science Foundation of China(52072124);Natural Science Foundation of Shanghai(20ZR1414900)

摘要/Abstract

摘要：

本研究发展了一种简便的“原位还原”策略构建负载银簇的硅基杂化纳米颗粒(Ag@SHNPs)。首先利用两亲性嵌段共聚物PS₈₉-b-PAA₁₆自组装行为和3-巯基丙基三甲氧基硅烷(MPTMS)在亲水链段PAA区域的水解缩聚反应形成有机硅胶束杂化纳米结构, 再利用有机硅骨架中丰富的巯基作为还原位点, 原位将银盐转化为银簇, 最终得到负载银簇的硅基杂化纳米颗粒, 并对该杂化纳米颗粒的形貌、结构以及成分组成作了分析。通过测试材料对不同细胞系的毒性验证了其良好的生物相容性。最后以4-巯基苯甲酸(4-MBA)为探针分子, 对硅基杂化颗粒基底的表面增强拉曼散射(SERS)活性进行检测。在532 nm波长的激光激发下, 4-MBA标记的硅基杂化纳米颗粒展示出明显的拉曼信号增强特性, 增强因子约为10⁵。因此, 该硅基杂化基底材料在SERS生物成像和高灵敏检测方面具有潜在的应用前景。

关键词: 银团簇, 限域空间, 原位还原, 表面增强拉曼散射

Abstract:

In this research, a facile “in-situ reduction” strategy was developed to construct silver clusters-loaded silica-based hybrid nanoparticles (Ag@SHNPs). Firstly, the formation of organosilica-micellar hybrid nanostructure was achieved by self-assembly of amphiphilic block copolymer PS₈₉-b-PAA₁₆and hydrolysis, and polycondensation of (3-mercaptopropyl)trimethoxysilane (MPTMS) on the hydrophilic PAA segment. Then, the abundant thiol groups in the organosilica framework were used as reduction sites to in-situ convert the silver salt into silver clusters, and finally the Ag@SHNPs were obtained. Morphology, structure and composition of the hybrid nanoparticles were analyzed, and their cytotoxicity on different cell lines were explored, showing good biocompatibility. The surface enhanced Raman scattering (SERS) activity of the Ag@SHNPs substrate were detected by using 4-mercaptobenzoic acid (4-MBA) as the probe molecule. Under an excitation wavelength of 532 nm laser, 4-MBA-labeled Ag@SHNPs exhibited obvious Raman enhanced signal with an enhancement factor of about 10⁵. Therefore, the silica-based hybrid substrate material shows potential application prospects in SERS bioimaging and high-sensitivity detection.

Key words: silver nanoclusters, confined space, in-situ reduction, surface enhanced Raman scattering

中图分类号:

TQ174

文子聪, 牛德超, 李永生. 负载银簇的硅基杂化纳米颗粒制备及其SERS性能[J]. 无机材料学报, 2021, 36(12): 1297-1304.

WEN Zicong, NIU Dechao, LI Yongsheng. Silver Clusters-loaded Silica-based Hybrid Nanoparticles: Synthesis and SERS Performance[J]. Journal of Inorganic Materials, 2021, 36(12): 1297-1304.

图/表 12

图1 Ag@SHNPs制备示意图

Fig. 1 Schematic illustration for the fabrication of Ag@SHNPs

图2 (a)PS89-b-PAA16胶束和对应SHNPs的水合动力学粒径分布, 以及(b)不同MPTMS用量(100、150、200 μL)下制备的SHNPs水合动力学粒径分布

Fig. 2 (a) Hydrodynamic diameter distributions of PS89-b- PAA16 micelles and SHNPs, and (b) hydrodynamic diameter distributions of SHNPs prepared with different amounts of MPTMS (100, 150, 200 μL)

图3 不同MPTMS用量下制备的SHNPs的透射电镜照片

Fig. 3 TEM images of SHNPs prepared with different amounts of MPTMS (a, d) 100 μL; (b, e) 150 μL; (c, f) 200 μL

图4 (a)巯基的标准曲线(插图为Ellman试剂与巯基反应示意图)与(b)不同SHNPs与Ellman试剂反应后混合溶液的紫外-可见吸收光谱

Fig. 4 (a) Standard curve of thiol groups with inset showing the reaction between Ellman’s agent and thiol groups, and (b) UV-Vis spectra of SHNPs mixed with Ellman’s agent

图5 Ag@SHNPs的透射电镜照片

Fig. 5 TEM images of Ag@SHNPs

图6 Ag@SHNPs 和4-MBA标记的Ag@SHNPs的扫描电镜照片(a, b)和能谱(c, d)

Fig. 6 SEM images (a, b) and energy-dispersive spectra (c, d) of Ag@SHNPs and Ag@SHNPs with 4-MBA

图7 SHNPs、4-MBA标记的SHNPs、Ag@SHNPs、4-MBA标记的SHNPs的(a)水合动力学粒径分布和(b)Zeta电位图, (c)CMs、SHNPs、Ag@SHNPs的FT-IR图谱, 以及(d)Ag@SHNPs、4-MBA标记的Ag@SHNPs的紫外-可见吸收光谱

Fig. 7 (a) Hydrodynamic diameter distributions and (b) histogram of Zeta potentials of SHNPs, SHNPs with 4-MBA, Ag@SHNPs, Ag@SHNPs with 4-MBA, (c) FT-IR spectra of CMs, SHNPs, Ag@SHNPs, and (d) UV-Vis spectra of Ag@SHNPs, Ag@SHNPs with 4-MBA

图8 Ag@SHNPs的XRD图谱

Fig. 8 XRD pattern of Ag@SHNPs

图9 (a)CMs、SHNPs、Ag@SHNPs在水中不同稀释倍数下的水合动力学粒径和(b)Ag@SHNPs 7 d内分散在RPMI 1640培养基和DMEM培养基中的水合动力学粒径

Fig. 9 (a) Hydrodynamic diameters of CMs, SHNPs, and Ag@SHNPs in water against dilution, and (b) hydrodynamic diameters of Ag@SHNPs dispersed in RPMI 1640 medium and DMEM medium in 7 d Colorful figures are available on website

图10 SMMC-7721细胞、NIH-3T3细胞、MEF细胞、HaCaT细胞与不同银浓度的(a)Ag@SHNPs、(b)4-MBA标记的Ag@SHNPs孵育24 h后的CCK-8细胞存活率

Fig. 10 CCK-8 cell viabilities of SMMC-7721, NIH-3T3, MEF, and HaCaT cells incubated with different Ag concentrations of (a) Ag@SHNPs and (b) Ag@SHNPs with 4-MBA for 24 h Colorful figures are available on website

图11 Ag@SHNPs、4-MBA标记的Ag@SHNPs以及纯4-MBA分子溶液在532 nm激发波长下的拉曼光谱图

Fig. 11 Raman spectra of Ag@SHNPs, Ag@SHNPs with 4-MBA and pure 4-MBA solution under 532 nm excitation

图12 SMMC-7721细胞与4-MBA标记的Ag@SHNPs共培养24 h后的拉曼光谱图

Fig. 12 Raman spectra of SMMC-7721 cells incubated with Ag@SHNPs with 4-MBA for 24 h

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负载银簇的硅基杂化纳米颗粒制备及其SERS性能

Silver Clusters-loaded Silica-based Hybrid Nanoparticles: Synthesis and SERS Performance

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