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Interactions Between Amino Acid-Tagged Naphthalenediimide and Single Walled Carbon Nanotubes for the Design and Construction of New Bioimaging Probes

机译:氨基酸标记的萘二酰亚胺与单壁碳纳米管之间的相互作用,用于新型生物成像探针的设计和构建

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摘要

A new synthetic route to functionalized single walled carbon nanotubes (SWNTs) via supramolecular interactions using a specifically designed naphthalenediimide (NDI) nanoreceptor is demonstrated. The tendency of the NDI to spontaneously form composites with carbon nanomaterials leads to fluorescent amino acid tagged SWNTs, which are dispersible in widely accessible organic solvents (CHCl_3, DMSO) as well as in biocompatible cell medium (EMEM, Eagle's modified essential medium). The X-ray crystal structure of the first iodine-tagged and amino acid-functionalized NDI molecule, designed especially to facilitate the high resolution transmission electron microscopy (HR TEM) imaging whilst retaining its ability to self-assemble into a nanodimensional receptor in weakly polar solvents, is also described. A new hybrid material, NDI@SWNT, was prepared and characterized as dispersed in organic solvents and aqueous media and in the solid state by HR TEM, tapping mode atomic force microscopy (TM AFM), scanning electron microscopy (SEM), circular dichroism, Raman and fluorescence spectroscopies (steady-state single and two-photon techniques). Combined microscopy techniques, density functional theory (DFT) calculations using the Spanish Initiative for Electronic Simulations with Thousands of Atoms (SIESTA) program and spectroscopic measurements in solution indicate that amino acid-functionalized NDI interacts strongly with SWNTs and forms a donor-acceptor complex. Density functional theory (DFT) calculations predicted the geometry and the binding energies of an NDI molecule loaded onto a SWNT strand and the possibility of charge transfer interactions within the hybrid. The NDI@SWNT composite translocates into cells (e.g. FEK-4, HeLa, MCF-7) as an intact object and localizes in the cells' cytoplasm and partially in the nucleus. The NDI coating enhances the biocompatibility of SWNTs and mediates its intracellular localization as shown by confocal fluorescence imaging and fluorescence lifetime imaging (FLIM) techniques. The excited state fluorescence lifetime of the probes in cells versus solution phase indicates that the probes remain unaffected by the change in their chemical environment within the experimental timescale (2 h).
机译:展示了使用特殊设计的萘二酰亚胺(NDI)纳米受体通过超分子相互作用合成功能化单壁碳纳米管(SWNT)的新合成途径。 NDI自发形成与碳纳米材料形成复合物的趋势导致了荧光氨基酸标记的单壁碳纳米管,可分散在广泛使用的有机溶剂(CHCl_3,DMSO)以及生物相容性细胞培养基(EMEM,Eagle's改良的基本培养基)中。第一个被碘标记和氨基酸官能化的NDI分子的X射线晶体结构,特别设计用于促进高分辨率透射电子显微镜(HR TEM)成像,同时保留其在弱极性中自组装成纳米受体的能力还描述了溶剂。制备了一种新的杂化材料NDI @ SWNT,并通过HR TEM,敲击模式原子力显微镜(TM AFM),扫描电子显微镜(SEM),圆二色性,拉曼光谱和荧光光谱法(稳态单光子和双光子技术)。结合显微镜技术,使用西班牙千原子电子模拟计划(SIESTA)程序进行的密度泛函理论(DFT)计算以及溶液中的光谱测量表明,氨基酸官能化的NDI与SWNT相互作用很强,并形成了供体-受体复合物。密度泛函理论(DFT)计算预测了加载到SWNT链上的NDI分子的几何形状和结合能,以及杂化物中电荷转移相互作用的可能性。 NDI @ SWNT复合物作为完整的对象转移到细胞中(例如FEK-4,HeLa,MCF-7),并位于细胞的细胞质中,部分位于细胞核中。 NDI涂层增强了单壁碳纳米管的生物相容性,并介导其在细胞内的定位,如共聚焦荧光成像和荧光寿命成像(FLIM)技术所示。探针在细胞中相对于溶液相的激发态荧光寿命表明,探针在实验时间内(2小时)不受化学环境变化的影响。

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  • 来源
    《Advanced Functional Materials》 |2012年第3期|p.503-518|共16页
  • 作者单位

    Department of Chemistry University of Bath Claverton Down, BA2 7AY, UK;

    Department of Chemistry University of Bath Claverton Down, BA2 7AY, UK;

    School of Chemistry University of Nottingham Nottingham, NG7 2RD UK;

    Department of Chemistry University of Bath Claverton Down, BA2 7AY, UK;

    Department of Chemistry Chemistry Research Laboratory University of Oxford Mansfield Road, Oxford, OX1 3TA, UK;

    Department of Chemistry University of Bath Claverton Down, BA2 7AY, UK;

    Department of Chemistry University of Bath Claverton Down, BA2 7AY, UK;

    Department of Materials BegbrokeNano University of Oxford, Oxford, UK;

    Central Laser Facility Rutherford Appleton Laboratory, Research Complex at Harwell, STFC Didcot, OX11 0QX, UK;

    Department of Pharmacy and Pharmacology University of Bath Claverton Down, BA2 7AY, UK;

    Central Laser Facility Rutherford Appleton Laboratory, Research Complex at Harwell, STFC Didcot, OX11 0QX, UK;

    Department of Chemistry University of Cambridge Lensfield Road, CB2 1 EW, Cambridge,UK;

    Department of Chemistry University of Bath Claverton Down, BA2 7AY, UK;

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