Fast proton transport enables the magnetic relaxation response of graphene quantum dots for monitoring the oxidative environment in vivo

Abstract

A magnetic relaxation switch (MRS) that targets small molecules such as H₂O₂ is difficult to realize because of the small size of the targets, which cannot gather enough MRS probes to form aggregates and generate a difference in magnetic relaxation times. Therefore, the development of small molecule-targeted MRS is strongly dependent on changes in the interfacial structure of the probe, which modulates the proton transport behavior near the probe. Herein, functionalized graphene quantum dots (GQDs) consisting of GQDs with disulfide bonds, polyethylene glycol (PEG), and paramagnetic Gd³⁺ were used as the MRS probe to sense H₂O₂. The structure of GQDs changed after reacting with H₂O₂. The PEG assembled a tube for transmitting changes in GQDs via proton transport and thus enabled the magnetic relaxation response of the probe towards H₂O₂. Pentaethylene glycol was experimentally and theoretically proven to have the strongest ability to transport protons. Such a probe can be applied in the differentiation of healthy and senescent cells/tissues using in vitro fluorescent imaging and in vivo magnetic resonance imaging. This work provides a reliable solution for building a proton transport route, which not only enables the response of the MRS probe towards the targets but also demonstrates the design of carbon nanostructures with proton transport behaviors.