纤维素纳米晶基一维SERS探针的制备及其细胞成像性能  

Synthesis of CNC based one⁃dimensional SERS probes and evaluation of cell imaging performance

作　　者：邓稳 翟珊珊 刘星月 李思婕 徐朝阳 张磊 吴伟兵 DENG Wen;ZHAI Shanshan;LIU Xingyue;LI Sijie;XU Zhaoyang;ZHANG Lei;WU Weibing(College of Light Industry and Food Engineering,Jiangsu Co-Innovation Center for Efficient Processing and Utilization of Forest Resources,Nanjing Forestry University,Nanjing 210037,China;College of Materials Science and Engineering,Nanjing Forestry University,Nanjing 210037,China;College of Materials Science and Engineering,Nanjing University of Posts and Telecommunications,Nanjing 210023,China)

机构地区：[1]南京林业大学轻工与食品学院,江苏省林业资源高效加工利用协同创新中心,南京210037 [2]南京林业大学材料科学与工程学院,南京210037 [3]南京邮电大学材料科学与工程学院,南京210023

出　　处：《林业工程学报》2025年第1期105-112,共8页Journal of Forestry Engineering

基　　金：江苏省研究生科研实践创新项目(KYCX22_1076);国家自然科学基金(62075103);江苏省自然科学基金(BK20211271)。

摘　　要：表面增强拉曼散射(SERS)技术已被广泛应用于生物成像领域,构筑具有高灵敏度、水中分散稳定性高和生物相容性的SERS探针,是实现高质量细胞生物成像的基础。以磺酸基纤维素纳米晶(CNC⁃SO_(3)H)为多功能载体,连续通过NaIO_(4)氧化和席夫碱反应在CNC⁃SO_(3)H的C2/C3羟基活性位点选择性引入聚乙二醇(PEG)和巯基基团,通过Au⁃S键自组装负载金纳米颗粒(AuNPs)构建一维“热点”结构,成功制备了纤维素纳米晶(CNC)基一维SERS探针并用于细胞SERS成像。通过透射电镜、傅里叶变换红外光谱、紫外可见光分光光度计和共聚焦拉曼显微镜等对探针的结构、形貌以及检测性能等进行分析。结果表明,由于CNC表面PEG长链的存在,CNC⁃PEG⁃SH@AuNPs在200 mmol/L的NaCl溶液中能表现出优异的分散稳定性。以4⁃巯基苯甲酸(4⁃MBA)作为拉曼信号分子,探针在10^(-6)mol/L浓度下依然能显示信号分子特征峰的拉曼信号,并且在0.1 mol/L磷酸缓冲盐溶液(PBS)中随时间变化的SERS信号表现出良好的灵敏度和重复性。将合成的SERS探针用于海拉(HeLa)细胞中,其细胞活力可维持在80%以上,并成功实现1075和1580 cm^(-1)双通道细胞SERS成像。Surface⁃enhanced Raman scattering(SERS)technology has been widely used in the field of bioimaging,and the synthesis of SERS probes with high sensitivity,high water dispersion stability and biocompatibility is the basis for realizing high⁃quality cellular bioimaging.In this study,using sulfonated cellulose nanocrystals(CNC⁃SO_(3)H)as a multifunctional carrier,poly(ethylene glycol)(PEG)and sulfhydryl groups were selectively introduced into the C2/C3 hydroxyl active sites of CNC⁃SO_(3)H by successive oxidation with NaIO_(4)and Schiff base reaction,and synthesized a one⁃dimensional“hotspot”structure by self⁃assembly loaded gold nanoparticles(AuNPs)through Au⁃S bonding,so that cellulose nanocrystals⁃based one⁃dimensional(1D)SERS probes were successfully prepared for cellular SERS imaging.The morphology of the probes was characterized by the transmission electron microscopy(TEM),and each CNC⁃PEG⁃SH@AuNPs probe was relatively independent from each other without large⁃scale aggregation,reflecting a well⁃dispersed 1D characteristic structure.The structures of the probes were analyzed by the Fourier transform infrared spectroscopy(FT⁃IR)and X⁃ray photoelectron spectroscopy(XPS)to verify the modification and loading of mercaptoethylamine,PEG and AuNPs on the CNC surface.In order to evaluate the aqueous dispersion stability of AuNPs and CNC⁃PEG⁃SH@AuNPs,the changes of their absorption spectra at different salt solution concentrations and presence times were investigated.The results of UV⁃Vis spectra showed that CNC⁃PEG⁃SH@AuNPs can effectively resist the salt ion⁃induced aggregation effect in 200 mmol/L NaCl solution,and the spectra of CNC⁃PEG⁃SH@AuNPs composites at 50 mmol/L salt ion concentration showed a completely unchanged state from 0 to 150 min,presenting a good dispersion stability.It can be stably dispersed in 0.1 mol/L PBS solution for several weeks.The SERS performance of CNC⁃PEG⁃SH@Au4⁃MBA NPs probes was evaluated.Using 4⁃mercaptobenzoic acid(4⁃MBA)as th

关 键 词：纤维素纳米晶 金纳米颗粒 聚乙二醇 SERS探针 HeLa细胞成像 

分 类 号：TQ35[化学工程]