4.8 Article

Metal-Bridged Graphene-Protein Supraparticles for Analog and Digital Nitric Oxide Sensing

Journal

ADVANCED MATERIALS
Volume 33, Issue 24, Pages -

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/adma.202007900

Keywords

fluorescent probes; graphene quantum dots; self‐ assembly; sensors; supraparticles

Funding

  1. National Natural Science Foundation of China [21834007, 21904087, 22004058, 21775044]
  2. National Key RAMP
  3. D Program of China [2016YFA0400900]
  4. Science and Technology Commission of Shanghai Municipality [19ZR1474600]
  5. China Postdoctoral Science Foundation [2018M641995]
  6. Key Research Program of Frontier Sciences [QYZDJ-SSW-SLH031]
  7. Open Large Infrastructure Research of CAS, Chinese Academy of Sciences
  8. LU Jiaxi International Team of the Chinese Academy of Sciences
  9. K. C. Wong Foundation at Shanghai Jiao Tong University
  10. Innovative research team of high-level local universities in Shanghai
  11. NSF [1463474, 1566460]

Ask authors/readers for more resources

This study successfully assembled highly uniform supraparticles from graphene quantum dots (GQDs) by bridging the components with Tb3+ ions, enhancing the transfer of excitonic energy from GQDs and proteins to Tb3+. The mechanism is activated by reducing Cu2+ to Cu1+ by nitric oxide (NO), which greatly improves the sensitivity of NO detection.
Self-limited nanoassemblies, such as supraparticles (SPs), can be made from virtually any nanoscale components, but SPs from nanocarbons including graphene quantum dots (GQDs), are hardly known because of the weak van der Waals attraction between them. Here it is shown that highly uniform SPs from GQDs can be successfully assembled when the components are bridged by Tb3+ ions supplementing van der Waals interactions. Furthermore, they can be coassembled with superoxide dismutase, which also has weak attraction to GQDs. Tight structural integration of multilevel components into SPs enables efficient transfer of excitonic energy from GQDs and protein to Tb3+. This mechanism is activated when Cu2+ is reduced to Cu1+ by nitric oxide (NO)-an important biomarker for viral pulmonary infections and Alzheimer's disease. Due to multipronged fluorescence enhancement, the limit of NO detection improves 200 times reaching 10 x 10(-12) m. Furthermore, the uniform size of SPs enables digitization of the NO detection using the single particle detection format resulting in confident registration of as few as 600 molecules mL(-1). The practicality of the SP-based assay is demonstrated by the successful monitoring of NO in human breath. The biocompatible SPs combining proteins, carbonaceous nanostructures, and ionic components provide a general path for engineering uniquely sensitive assays for noninvasive tracking of infections and other diseases.

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