Shape-changing magnetic assemblies as high-sensitivity NMR-readable nanoprobes

Abstract

Fluorescent and plasmonic labels and sensors have revolutionized molecular biology, helping visualize in vitro cellular and biomolecular processes ^{1– 3} . Increasingly, such probes are now designed to respond to wavelengths in the near infrared region, where reduced tissue autofluorescence and photon attenuation enable subsurface in vivo sensing ⁴ . But even in the near infrared, optical resolution and sensitivity decrease rapidly with increasing depth. Here we present a sensor design that obviates the need for optical addressability by operating in the NMR radio-frequency (RF) spectrum, where signal attenuation and distortion by tissue and biological media are negligible, where background interferences vanish, and where sensors can be spatially located using standard magnetic resonance imaging (MRI) equipment. The RF-addressable sensor assemblies presented here are comprised of pairs of magnetic disks spaced by swellable hydrogel material; they reversibly reconfigure in rapid response to chosen stimuli, to give geometry-dependent, dynamic NMR spectral signatures. Sensors can be made from biocompatible materials, are detectable down to low concentrations, and offer potential responsive NMR spectral shifts approaching a million times those of traditional magnetic resonance spectroscopies. Inherent adaptability should allow such shape-changing systems to measure numerous different environmental and physiological indicators, affording broadly generalizable, MRI-compatible, RF analogues to optically-based probes for use in basic chemical, biological and medical research.