New structural characteristics emerge when solid-state crystals are constructed in lower dimensions. This is exemplified by single-wall carbon nanotubes, which exhibit a degree of freedom in handedness and a multitude of helicities that give rise to three distinct types of electronic structures: metals, quasi-metals, and semiconductors. Here we report the use of intrinsically chiral single-stranded DNA to achieve simultaneous handedness and helicity control for all three types of nanotubes. We apply polymer aqueous two-phase systems to select special DNA-wrapped carbon nanotubes, each of which we argue must have an ordered DNA structure that binds to a nanotube of defined handedness and helicity and resembles a well-folded biomacromolecule with innate stereoselectivity. We have screened over 300 short single-stranded DNA sequences with palindrome symmetry, leading to the selection of more than 20 distinct carbon nanotube structures that have defined helicity and handedness and cover the entire chiral angle range and all three electronic types. The mechanism of handedness selection is illustrated by a DNA sequence that adopts two distinct folds on a pair of (6,5) nanotube enantiomers, rendering them large differences in fluorescence intensity and chemical reactivity. This result establishes a first example of functionally distinguishable left- and right-handed carbon nanotubes. Taken together, our work demonstrates highly efficient enantiomer differentiation by DNA and offers a first comprehensive solution to achieve simultaneous handedness and helicity control for all three electronic types of carbon nanotubes.
This work expands the redox chemistry of single-wall carbon nanotubes (SWCNTs) by investigating its role in a number of SWCNT sorting processes. Using a polyethylene glycol (PEG)/dextran (DX) aqueous two-phase system, we show that electron-transfer between redox molecules and SWCNTs triggers reorganization of the surfactant coating layer, leading to strong modulation of nanotube partition in the two phases. While the DX phase is thermodynamically more favored by an oxidized SWCNT mixture, the mildly reducing PEG phase is able to recover SWCNTs from oxidation and extract them successively from the DX phase. Remarkably, the extraction order follows SWCNT bandgap: semiconducting nanotubes of larger bandgap first, followed by semiconducting nanotubes of smaller bandgap, then nonarmchair metallic tubes of small but nonvanishing bandgap, and finally armchair metallic nanotubes of zero bandgap. Furthermore, we show that redox-induced surfactant reorganization is a common phenomenon, affecting nanotube buoyancy in a density gradient field, affinity to polymer matrices, and solubility in organic solvents. These findings establish redox modulation of surfactant coating structures as a general mechanism for tuning a diverse range of SWCNT sorting processes and demonstrate for the first time that armchair and nonarmchair metallic SWCNTs can be separated by their differential response to redox.
Precise fabrication of semiconducting carbon nanotubes (CNTs) into densely aligned evenly spaced arrays is required for ultrascaled technology nodes. We report the precise scaling of inter-CNT pitch using a supramolecular assembly method called spatially hindered integration of nanotube electronics. Specifically, by using DNA brick crystal-based nanotrenches to align DNA-wrapped CNTs through DNA hybridization, we constructed parallel CNT arrays with a uniform pitch as small as 10.4 nanometers, at an angular deviation <2° and an assembly yield >95%.
We have measured peak and spectrally integrated absolute absorption cross sections for the first (E11) and second (E22) optical transitions of seven semiconducting single-walled carbon nanotube (SWCNT) species in bulk suspensions. Species-specific concentrations were determined using short-wave IR fluorescence microscopy to directly count SWCNTs in a known sample volume. Measured cross sections per atom are inversely related to nanotube diameter. E11 cross sections are larger for mod 1 species than for mod 2; the opposite is found for E22.
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