Helical Assembly of Flavin Mononucleotides on Carbon Nanotubes as Multimodal Near-IR Hg(II)-Selective Probes

Abstract

The development of novel methods to detect mercury is of paramount importance owing to the impact of this metal on human health and the environment. We observed that flavin mononucleotide (FMN) and its helical assembly with a single-walled carbon nanotube (SWNT) selectively bind Hg2+ arising from HgCl2 and MeHgCl. Absorption spectroscopic studies show that FMN preferentially forms a 2:1 rather than a 1:1 complex with Hg2+ at high FMN concentrations. On the basis of the analogy to the thymine-Hg-thymine complex, it is proposed that the 2:1 complex between FMN and Hg2+ comprises a Hg-bridged pair of FMN groups, regardless of the presence of SWNT. Upon addition of as little as a few hundred nanomoles of Hg2+, both FMN and FMNSWNT exhibit absorption and photoluminescence (PL) changes. Moreover, FMN-SWNT displays simultaneous multiple sigmoidal changes in PL of SWNT tubes having different chiral vectors. Assessment of binding affinities using the Hill equation suggests that 2:1 and 1:1 complexes form between Hg2+ and FMN groups on the FMNSWNT. Theoretical calculations indicate that optical changes of the FMNSWNT originate from Hg-mediated conformational changes occurring on the helical array of FMN on the SWNT. High-resolution transmission electron microscopy revealed that the presence of Hg2+ in complexes with the FMN-SWNT enables visualization of helical periodic undulation of FMN groups along SWNT without the need for staining. Circular dichroism (CD) study revealed that FMN-SWNT whose CD signal mainly originates from FMN decreases dichroic bands upon the addition of Hg2+ owing to the formation of a centrosymmetric FMN-Hg-FMN triad on SWNT. The binding mode specificity and multimodal changes observed in response to Hg2+ ions suggest that systems based on FMN-SWNT can serve as in vivo NIR beacons for the detection of various mercury derivatives.