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

Abstract

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 Ã 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.Graphene quantum dots (GQDs) can assemble into self- limited supraparticles when van der Waals forces are supplemented by coordination bonds with Tb3+ ions. Superoxide dismutase (SOD) is incorporated into supraparticles, which enables a selective assay for nitric oxide (NO) with ultrahigh sensitivity. Practical for NO detection in exhaled breath, a rapid non- invasive test is approached for pulmonary inflammation, such as coronavirus pneumonia.