Noncovalent interactions between single-stranded DNA (ssDNA) oligonucleotides and single wall carbon nanotubes (SWNTs) have provided a unique class of tunable chemistries for a variety of applications. However, mechanistic insight into both the photophysical and intermolecular phenomena underlying their utility is lacking, which results in obligate heuristic approaches for producing ssDNA-SWNT based technologies. In this work, we present an ultrasensitive "turn-on" nanosensor for neuromodulators dopamine and norepinephrine with strong relative change in fluorescence intensity (Δ F/ F₀) of up to 3500%, a signal appropriate for in vivo neuroimaging, and uncover the photophysical principles and intermolecular interactions that govern the molecular recognition and fluorescence modulation of this nanosensor synthesized from the spontaneous self-assembly of (GT)₆ ssDNA rings on SWNTs. The fluorescence modulation of the ssDNA-SWNT conjugate is shown to exhibit remarkable sensitivity to the ssDNA sequence chemistry, length, and surface density, providing a set of parameters with which to tune nanosensor dynamic range, analyte selectivity and strength of fluorescence turn-on. We employ classical and quantum mechanical molecular dynamics simulations to rationalize our experimental findings. Calculations show that (GT)₆ ssDNA form ordered rings around (9,4) SWNTs, inducing periodic surface potentials that modulate exciton recombination lifetimes. Further evidence is presented to elucidate how dopamine analyte binding modulates SWNT fluorescence. We discuss the implications of our findings for SWNT-based molecular imaging applications.

Redox-active proanions of the type B12(OCH2Ar)12 [Ar = C6F5 (1), 4-CF3C6H4 (2), 3,5-(CF3)2C6H3 (3)] are introduced in the context of an experimental and computational study of the visible-light-initiated polymerization of a family of styrenes. Neutral, air-stable proanions 1-3 were found to initiate styrene polymerization through single-electron oxidation under blue-light irradiation, resulting in polymers with number-average molecular weights (Mn) ranging from ∼6 to 100 kDa. Shorter polymer products were observed in the majority of experiments, except in the case of monomers containing 4-X (X = F, Cl, Br) substituents on the styrene monomer when polymerized in the presence of 1 in CH2Cl2. Only under these specific conditions are longer polymers (>100 kDa) observed, strongly supporting the formulation that reaction conditions significantly modulate the degree of ion pairing between the dodecaborate anion and cationic chain end. This also suggests that 1-3 behave as weakly coordinating anions (WCA) upon one-electron reduction because no incorporation of the cluster-based photoinitiators is observed in the polymeric products analyzed. Overall, this work is a conceptual realization of a single reagent that can serve as a strong photooxidant, subsequently forming a WCA.