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基于具有锰锌铁氧体核的有机功能化金纳米壳的多模态造影剂实现pH传感

Multimodal Contrast Agent Enabling pH Sensing Based on Organically Functionalized Gold Nanoshells with Mn-Zn Ferrite Cores.

作者信息

Bui Duong Thuy, Havelek Radim, Královec Karel, Kubíčková Lenka, Kuličková Jarmila, Matouš Petr, Herynek Vít, Kupčík Jaroslav, Muthná Darina, Řezanka Pavel, Kaman Ondřej

机构信息

Institute of Physics, Czech Academy of Sciences, Cukrovarnická 10, 162 00 Prague, Czech Republic.

Department of Analytical Chemistry, University of Chemistry and Technology, Technická 5, 166 28 Prague, Czech Republic.

出版信息

Nanomaterials (Basel). 2022 Jan 27;12(3):428. doi: 10.3390/nano12030428.

DOI:10.3390/nano12030428
PMID:35159772
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC8839728/
Abstract

Highly complex nanoparticles combining multimodal imaging with the sensing of physical properties in biological systems can considerably enhance biomedical research, but reports demonstrating the performance of a single nanosized probe in several imaging modalities and its sensing potential at the same time are rather scarce. Gold nanoshells with magnetic cores and complex organic functionalization may offer an efficient multimodal platform for magnetic resonance imaging (MRI), photoacoustic imaging (PAI), and fluorescence techniques combined with pH sensing by means of surface-enhanced Raman spectroscopy (SERS). In the present study, the synthesis of gold nanoshells with Mn-Zn ferrite cores is described, and their structure, composition, and fundamental properties are analyzed by powder X-ray diffraction, X-ray fluorescence spectroscopy, transmission electron microscopy, magnetic measurements, and UV-Vis spectroscopy. The gold surface is functionalized with four different model molecules, namely thioglycerol, -2,3-dimercaptosuccinate, 11-mercaptoundecanoate, and (11-mercaptoundecyl)-,,-trimethylammonium bromide, to analyze the effect of varying charge and surface chemistry on cells in vitro. After characterization by dynamic and electrophoretic light scattering measurements, it is found that the particles do not exhibit significant cytotoxic effects, irrespective of the surface functionalization. Finally, the gold nanoshells are functionalized with a combination of 4-mercaptobenzoic acid and 7-mercapto-4-methylcoumarin, which introduces a SERS active pH sensor and a covalently attached fluorescent tag at the same time. H NMR relaxometry, fluorescence spectroscopy, and PAI demonstrate the multimodal potential of the suggested probe, including extraordinarily high transverse relaxivity, while the SERS study evidences a pH-dependent spectral response.

摘要

将多模态成像与生物系统中物理性质传感相结合的高度复杂的纳米颗粒可以显著增强生物医学研究，但同时展示单个纳米尺寸探针在多种成像模态下的性能及其传感潜力的报告却相当稀少。具有磁芯和复杂有机功能化的金纳米壳可能为磁共振成像（MRI）、光声成像（PAI）以及通过表面增强拉曼光谱（SERS）进行pH传感相结合的荧光技术提供一个高效的多模态平台。在本研究中，描述了具有Mn-Zn铁氧体磁芯的金纳米壳的合成，并通过粉末X射线衍射、X射线荧光光谱、透射电子显微镜、磁性测量和紫外-可见光谱分析了它们的结构、组成和基本性质。金表面用四种不同的模型分子进行功能化，即硫代甘油、-2,3-二巯基琥珀酸、11-巯基十一烷酸和(11-巯基十一烷基)-、、-三甲基溴化铵，以分析电荷和表面化学变化对体外细胞的影响。通过动态和电泳光散射测量进行表征后，发现无论表面功能化如何，这些颗粒都没有表现出显著的细胞毒性作用。最后，金纳米壳用4-巯基苯甲酸和7-巯基-4-甲基香豆素的组合进行功能化，这同时引入了一个SERS活性pH传感器和一个共价连接的荧光标签。1H NMR弛豫测量、荧光光谱和PAI证明了所建议探针的多模态潜力，包括极高的横向弛豫率，而SERS研究证明了pH依赖性光谱响应。

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