(Invited) Sensing with Chirality Pure Near Infrared Fluorescent Carbon Nanotubes

Abstract

Semiconducting single wall carbon nanotubes (SWCNTs) fluoresce in the near infrared (NIR) and the emission wavelength depends on their chirality (n,m). Interactions with the environment affect the fluorescence and can be tailored by functionalizing SWCNTs with biopolymers such as DNA, which is the basis for fluorescent biosensors. So far, such biosensors were mainly assembled from mixtures of SWCNT chiralities with large spectral overlap, which affects sensitivity as well as selectivity and prevents multiplexed sensing. The main challenge to gain chirality pure sensors has been to combine approaches to isolate specific SWCNTs and generic (bio)functionalization approaches. Here, we created chirality pure SWCNT-based NIR biosensors for important analytes such as neurotransmitters and investigated the impact of SWCNT chirality/handedness as well as long-term stability and sensitivity. For this purpose, we used aqueous two-phase extraction (ATPE) to gain chirality pure (6,5)-, (7,5)-, (9,4)- and (7,6)-SWCNTs (emission at ~ 990, 1040, 1115 and 1130 nm). Exchange of the surfactant sodium deoxycholate (DOC) to specific single-stranded (ss)DNA sequences yielded monochiral sensors for small analytes (dopamine, riboflavin, ascorbic acid, pH). DOC residues impaired sensitivity and therefore sufficient removal was necessary. The assembled monochiral sensors were up to 10 times brighter than their non-purified counterparts and the ssDNA sequence determined absolute fluorescence intensity as well as colloidal (long-term) stability and selectivity for the analytes. (GT)40-(6,5)-SWCNTs displayed the maximum fluorescence response to the neurotransmitter dopamine (+140 %, Kd = 1.9 x10-7 M) and a long-term stability > 14 days. The specific ssDNA sequences imparted selectivity to the analytes in majority of the cases independent of SWCNT chirality and handedness of (+/-) (6,5)-SWCNTs, which allows a predictable design. Finally, multiple monochiral/single-color SWCNTs were combined to achieve ratiometric/multiplexed sensing of the important analytes dopamine, riboflavin, H2O2 and pH. In summary, we demonstrated the assembly, characteristics and potential of monochiral (single-color) SWCNTs for multiple NIR fluorescent sensing applications.